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Supplementary Information Double Carbonylation of Aryl Iodides with Amines under an Atmospheric Pressure of Carbon Monoxide Using Sulfur-Modified Au-Supported Palladium Nozomi Saito, a,c * Takahisa Taniguchi, a Naoyuki Hoshiya, b,d Satoshi Shuto, b Mitsuhiro Arisawa, b,c,e * Yoshihiro Sato a,c * a Laboratory of Fine Synthetic Chemistry, Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan b Laboratory of Organic Chemistry for Drug Development, Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan c ACT-C, Japan Science and Technology Agency (JST), Sapporo 060-0812, Japan d Present address: Kyoto Pharmaceutical University, Misasagi, Yamashina, Kyoto 607-8412, Japan e Present address: Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamada-oka, Suita, Osaka 565-0862, Japan S2~S13 : Experimental Procedure and Spectral Data S14~S98 : Charts of 1 H and 13 C NMR spectra of α-ketoamides 3 and mono-amides 4 ~ S1 ~ Electronic Supplementary Material (ESI) for Green Chemistry. This journal is © The Royal Society of Chemistry 2015

Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

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Page 1: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

Supplementary Information

Double Carbonylation of Aryl Iodides with Amines under an Atmospheric Pressure of

Carbon Monoxide Using Sulfur-Modified Au-Supported Palladium

Nozomi Saito,a,c* Takahisa Taniguchi,a Naoyuki Hoshiya,b,d Satoshi Shuto,b Mitsuhiro Arisawa,b,c,e*

Yoshihiro Satoa,c*

a Laboratory of Fine Synthetic Chemistry, Faculty of Pharmaceutical Sciences, Hokkaido University,

Sapporo 060-0812, Japan

b Laboratory of Organic Chemistry for Drug Development, Faculty of Pharmaceutical Sciences,

Hokkaido University, Sapporo 060-0812, Japan

c ACT-C, Japan Science and Technology Agency (JST), Sapporo 060-0812, Japan

d Present address: Kyoto Pharmaceutical University, Misasagi, Yamashina, Kyoto 607-8412, Japan

e Present address: Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamada-oka,

Suita, Osaka 565-0862, Japan

S2~S13 : Experimental Procedure and Spectral Data

S14~S98 : Charts of 1H and 13C NMR spectra of α-ketoamides 3 and mono-amides 4

~ S1 ~

Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2015

Page 2: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

General Information

All manipulations were performed under an argon atmosphere unless stated otherwise. Solvents

were purified under argon using The Ultimate Solvent System (Glass Counter Inc.) (CH3CN, DMF,

THF, Toluene). All other solvents and reagents were purified when necessary by standard

procedures. Column chromatography was performed on silica gel 60 N (spherical, neutral; Kanto

Kagaku, 45-50 μm) with the indicated solvent as eluent. TLC and PTLC were performed on Silica

gel 60 PF254 (Merck). IR spectra were obtained on a JASCO FT/IR 460Plus spectrometer. 1H NMR

spectroscopy was recorded on JEOL ECA500 (500 MHz) NMR spectrometer. Chemical shifts are

reported in ppm from the solvent as the internal standard (CDCl3: δ = 7.26 ppm). Data are reported

as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, br = broad, m =

multiplet), coupling constants (Hz) and integration. 13C NMR spectroscopy was recorded on JEOL

ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

the internal standard (CDCl3: δ = 77.00 ppm). Mass spectra were obtained on JEOL JMS-T100LP

and JMS-T100GCV and JEOL JMS-FAB mate mass spectrometer, and Thermo Scientific Exactive

mass spectrometer. GC was performed using a gas chromatograph Shimadzu GC-17A equipped

with an Agilent J&W DB-5MS column and a FID detector. Sulfur-Modified Au-Supported Pd

(SAPd) Material was prepared according to the literature.1

1 M. Al-Amin, S. Arai, N. Hoshiya, T. Honma, Y. Tamenori, T. Sato, M. Yokoyama, A. Ishii, M. Takeuchi, T.Maruko, S. Shuto, M. Arisawa, J. Org. Chem. 2013, 78, 7575-7581.

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Page 3: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

Experimental Procedure for Double Carbonylation Using SAPd Shown in Scheme 1

A flame-dried test tube was charged with 1a (117.8 mg, 0.503 mmol), K2CO3 (138.7 mg, 1.00 mmol), bibenzyl (48.9 mg, 0.268 mmol, as an internal standard) and degassed DMF (3 mL). To this were added a sheet of SAPd and 2a (130.0 µL, 1.49 mmol), and the test tube was immersed in a liquid nitrogen bath. After the mixture had been frozen, the flask was evacuated to 0.05 mmHg. The flask was backfilled with CO in a plastic balloon and the frozen mixture was thawed at room temperature. Then, the resulting reaction mixture was heated at 80 °C for 24 hours and analyzed by GC with an internal standard (bibenzyl). GC Yield (3aa: 40%, 4aa: 9%, 1a: 47%). After the reaction, the immobilized Pd NPs seemed to come off the Au-mesh, and the precipitation of Pd-black was observed in the reaction mixture as following pictures.

Typical Procedure for Double Carbonylation Using SAPd (Scheme 2). A mixture of 1a (117.0 mg, 0.500 mmol), K2CO3 (137.6 mg, 1.00 mmol), bibenzyl (43.5 mg, 0.239 mmol, internal standard for GC analysis) and a sheet of SAPd in DMF (3 mL) was heated at 80 °C for 2 hours under an argon atmosphere without stirring (1 atm). After removal of SAPd from the reaction vessel, 2a (130.0 µL, 1.49 mmol) and a stirring bar were added to the vessel. The vessel was immersed in a liquid nitrogen bath. After the mixture had been frozen, the flask was evacuated to 0.05 mmHg. The flask was backfilled with CO in a plastic balloon and the frozen mixture was thawed at room temperature. Then, the resulting reaction mixture was stirred at 80 °C for 24 hours. To the mixture was added 10% HCl at 0 °C, and the aqueous layer was extracted with AcOEt. The organic layer was dried over Na2SO4 and concentrated. The residue was purified by flash column chromatography on silica gel (hexane/AcOEt = 1/1~1/2) to give 3aa (106.0 mg, 85%) as a colorless solid and 4aa (11.7 mg, 11%) as a yellow oil, respectively. 1H and 13C NMR data of 1-(4-Methoxyphenyl)-2-morpholinoethane-1,2-dione (3aa): 1H NMR (500 MHz, CDCl3) δ 7.94-7.92 (m, 2H), 6.99-6.97 (m, 2H), 3.89 (s, 3H), 3.78 (m, 4H), 3.65 (t, J = 4.9 Hz, 2H), 3.38 (t, J = 4.9 Hz, 2H); 13C NMR(125 MHz, CDCl3) δ 189.8, 165.8, 165.0, 132.1, 126.1, 114.4, 66.8, 66.7, 55.7, 46.3, 41.5. These data were identical to those reported previously.2 1H and 13C NMR data of N-(4-Methoxybenzoyl)morpholine (4aa): 1H NMR (500 MHz, CDCl3) δ 7.38-7.36 (m, 2H), 2 J. Liu, R. Zhang, S. Wang, W. Sun, C. Xia, Org. Lett. 2009, 11. 1321-1324.

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Page 4: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

6.91-6.89 (m, 2H), 3.81 (s, 3H), 3.85-3.33 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 170.4, 160.8, 129.2, 127.3, 113.7, 66.9, 55.3, 48.2 (br), 43.0 (br). These data were identical to those reported previously.3

1-(4-Methoxyphenyl)-2-pyrrolidin-1-ylethane-1,2-dione (3ab) and N-(4-Methoxybenzoyl)- pyrrolidine (4ab) (Table 1, run 1). A crude product, which was obtained from 1a (117.4 mg, 0.502 mmol), K2CO3 (139.1 mg, 1.01 mmol), 2b (123.0 µL, 1.50 mmol), and bibenzyl (47.3 mg, 0.260 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/2) to give 3ab (95.7 mg, 82%) as a colorless solid and 4ab (10.4 mg, 10%) as a colorless solid, respectively. 1H and 13C NMR data of 3ab: 1H NMR (500 MHz, CDCl3) δ 7.93-7.90 (m, 2H), 6.93-6.91 (m, 2H), 3.83 (s, 3H), 3.59 (t, J = 6.7 Hz, 2H), 3.36 (t, J = 6.7 Hz, 2H), 1.93-1.85 (m, 4H); 13C NMR (125 MHz, CDCl3) δ 190.2, 165.2, 164.6, 132.2, 125.8, 114.1, 55.5, 46.5, 45.0, 25.8, 23.9. These data were identical to those reported previously.4 1H and 13C-NMR data of 4ab: 1H NMR (500 MHz, CDCl3) δ 7.52-7.50 (m, 2H), 6.90-6.88 (m, 2H), 3.83 (s, 3H), 3.64-3.62 (m, 2H), 3.49-3.46 (m, 2H), 1.90-1.85 (m, 4H); 13C NMR (125 MHz, CDCl3) δ 169.4, 160.7, 129.4, 129.1, 113.4, 55.3, 49.8, 46.3, 26.5, 24.4. These data were identical to those reported previously.5

1-(4-Methoxyphenyl)-2-piperidin-1-ylethane-1,2-dione (3ac) and N-(4-Methoxybenzoyl)- piperidine (4ac) (Table 1, run 2). A crude product, which was obtained from 1a (117.8 mg, 0.503 mmol), K2CO3 (137.6 mg, 0.996 mmol), bibenzyl (50.8 mg, 0.279 mmol, internal standard for GC analysis), and 2c (150.0 µL, 1.52 mmol) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/2) to give 3ac (117.3 mg, 94%) as a yellow oil and 4ac (7.0 mg, 6%) as a yellow oil, respectively. 1H and 13C NMR data of 3ac: 1H NMR (500 MHz, CDCl3) δ 7.89-7.86 (m 2H), 7.00-6.93 (m, 2H), 3.85 (s, 3H), 3.67-3.64 (m, 2H), 3.26-3.24 (m, 2H), 1.66-1.64 (m, 4H), 1.51-1.49 (m, 2H); 13C NMR (125 MHz, CDCl3) δ 190.6, 165.7, 164.7, 131.9, 126.2, 114.2, 55.5, 46.9, 41.9, 26.1, 25.3, 24.3. These data were identical to those reported previously.6 1H and 13C NMR data of 4ac: 1H NMR (500 MHz, CDCl3) δ 7.36 (d, J = 8.6 Hz, 2H), 6.89 (d, J = 8.6 Hz, 2H), 3.82 (s, 3H), 3.85-3.3.21 (br, 4H), 1.85-1.40 (br, 6H); 13C NMR (125 MHz, CDCl3) δ 170.3, 160.5, 128.8, 128.6, 113.6, 55.3, 49.0 (br), 43.4 (br), 26.4 (br), 25.7 (br), 24.6. These data were identical to those reported previously.7

1-(4-Methoxyphenyl)-2-(4-methylpiperazin-1-yl)ethane-1,2-dione (3ad) and 1-(4-Methoxy- benzoyl)-4-methylpiperazine (4ad) (Table 1, run 3). A crude product, which was obtained from 1a (119.9 mg, 0.512 mmol), K2CO3 (138.4 mg, 1.00 mmol)、2d (166.0 µL, 1.50 mmol), and bibenzyl (46.8 mg, 0.257 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (AcOEt/MeOH = 100/1~1/1) to give 3ad (115.4 mg, 86%) as a yellow oil and 4ad (13.8 mg, 11%) as a yellow oil, respectively. Spectral data of 3ad: IR (neat) 1637, 1599 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.88-7.85 (m, 2H), 6.95-6.93 (m, 2H), 3.85 (s, 3H), 3.85-3.82 (m, 2H), 3.44-3.42 (m, 2H), 2.64 (t, J = 5.2 Hz, 2H), 2.52 (t, J = 5.2 Hz, 2H), 2.38 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 189.8, 165.6, 164.9, 132.0, 125.8, 114.3, 55.6, 54.4, 54.0, 45.4, 45.0, 40.3; EI-LRMS m/z 262 (M+), 135; EI-HRMS calcd for 3 J. R. Martinelli, D. A. Watson, D. M. M. Freckmann, T. E. Barder, S. L. Buchwald, J. Org. Chem. 2008, 73, 7102-7107. 4 M. Iizuka, Y. Kondo, Chem. Commun. 2006, 1739-1741. 5 K. Ekoue-Kovi, C. Wolf, Org. Lett. 2007, 9, 3429-3432. 6 J. Zhang, Y. Wei, S. Lin, F. Liang, P. Liu, Org. Biomol. Chem. 2012, 10, 9237-9242. 7 J. Li, F. Xu, Y. Zhang, Q. Shen, J. Org. Chem. 2009, 74, 2575-2577.

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Page 5: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

C14H18O3N2 262.1317, found 262.1326. Spectral data of 4ad: IR (neat): 1626, 1610; 1H NMR (500 MHz, CDCl3) δ 7.38 (d, J = 8.6 Hz, 2H), 6.91 (d, J = 8.6 Hz, 2H), 3.83 (s, 3H), 3.63-3.47 (br, 4H), 2.48-2.35 (br, 4H), 2.32 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 170.3, 160.9, 129.1, 128.2, 113.8, 55.4, 55.3, 55.1, 46.0; EI-LRMS m/z 234 (M+), 135; EI-HRMS calcd for C13H18N2O2 234.13683, found 234.13675.

1-(4-Methoxyphenyl)-2-(1,4-dioxa-8-azaspiro[4.5]decan-8-yl)ethane-1,2-dione (3ae) and 1-(4-Methoxybenzoyl)-4-piperidone ethylene ketal (4ae) (Table 1, run 4). A crude product, which was obtained from 1a (118.5 mg, 0.506 mmol), K2CO3 (139.7 mg, 1.01 mmol), 2e (166.0 µL, 1.50 mmol), and bibenzyl (49.6 mg, 0.272 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/2) to give 3ae (134.9 mg, 87%) as a colorless solid and 4ae (12.6 mg, 9%) as a colorless oil, respectively. Spectral data of 3ae: mp 127 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1671, 1639, 1600 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.89 (d, J = 9.2 Hz, 2H), 6.95 (d, J = 9.2 Hz, 2H), 3.99-3.92 (m, 4H), 3.86 (s, 3H), 3.82 (t, J = 5.7 Hz, 2H), 3.40 (t, J = 5.7 Hz, 2H), 1.79 (t, J = 5.7 Hz, 2H), 1.66 (t, J = 5.7 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 190.3, 165.7, 164.8, 132.0, 126.1, 114.3, 106.6, 64.5, 55.6, 44.0, 39.2, 35.3, 34.6; EI-LRMS m/z 305 (M+), 135; EI-HRMS calcd for C16H19NO5 305.1263, found 305.1249. 1H and 13C NMR data of 4ae: 1H NMR (500 MHz, CDCl3) δ 7.33-7.32 (m, 2H), 6.86-6.84 (m, 2H), 3.92 (s, 4H), 3.76 (s, 3H), 3.80-3.40 (br, 4H), 1.83-1.42 (br, 4H); 13C NMR (125 MHz, CDCl3) δ 170.1, 160.5, 128.7, 127.9, 113.5, 106.8, 64.3, 55.1, 45.7 (br), 40.3 (br), 35.3 (br), 34.9 (br) These data were identical to those reported previously.8

1-[3,4-Dihydroisoquinolin-2(1H)-yl]-2-(4-methoxyphenyl)ethane-1,2-dione (3af) (Table 1, run 5). A crude product, which was 1a (117.4 mg, 0.502 mmol), K2CO3 (138.5 mg, 1.00 mmol), 2f (190.0 µL, 1.49 mmol), and bibenzyl (47.6 mg, 0.261 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 3/2~0/1) to give 3af (150.9 mg, quant) as a colorless solid. 1H and 13C NMR data of 3af: 1H NMR (500 MHz, CDCl3) δ 7.96-7.91 (m, 2H), 7.25-6.93 (m, 6H), 4.89 (s, 1.3H), 4.53 (s, 0.7H), 3.97 (t, J = 6.0 Hz, 0.7H), 3.88 (s, 1.9H), 3.86 (s, 1.1H), 3.61 (t, J = 6.0 Hz, 1.3H), 2.99 (t, J = 6.0 Hz, 0.7H), 2.85 (t, J = 6.0 Hz, 1.3H); 13C NMR (125 MHz, CDCl3) δ 190.1, 190.0, 166.4, 166.0, 164.9, 164.8, 133.4, 132.1, 131.8, 128.9, 128.7, 127.1, 126.7, 126.6, 126.5, 126.1, 126.0, 114.3, 55.6, 47.3, 43.4, 43.3, 39.2, 29.2, 28.2. These data were identical to those reported previously.9

N-Butyl-4-methoxyphenylglyoxamide (3ag) and N-Butyl-4-methoxyphenylbenzamide (4ag) (Table 1, run 6). A crude product, which was obtained from 1a (117.5 mg, 0.502 mmol), K2CO3 (139.3 mg, 1.01 mmol), 2g (148.0 µL, 1.50 mmol), and bibenyl (47.1 mg, 0.258 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 6/1) to give 3ag (87.8 mg, 74%) as a colorless solid and 4ag (23.4 mg, 22%) as a yellow oil, respectively. 1H and 13C NMR data of 3ag: 1H NMR (500 MHz, CDCl3) δ 8.42 (d, J = 8.8 Hz, 2H), 7.12 (brs, 1H), 6.95 (d, J = 8.8 Hz, 2H), 3.89 (s, 3H), 3.40-3.36 (m, 2H), 1.62-1.56 (m, 2H), 1.44-1.37 (m, 2H), 0.96 (t, J = 7.2 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 185.8, 164.6, 162.3, 133.8, 126.3, 113.7, 55.5, 39.0, 31.3, 20.0, 13.6. These data were identical to those reported previously4

1H and 13C NMR data of 4ag: 1H NMR (500 MHz,

8 D. L. Boger, M. D. Mullican, J. Org. Chem. 1984, 49, 4033-4044. 9 M. Genelot, N. Villandier, A. Bendjeriou, P. Jaithong, L. Djakovitch, V. Dufaud, Catal. Sci. Technol. 2012, 2, 1886-1893.

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Page 6: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

CDCl3) δ 7.73-7.71 (m, 2H), 6.92-6.91 (m, 2H), 6.02 (brs, 1H), 3.85 (s, 3H), 3.46-3.42 (m, 2H), 1.62-1.56 (m, 2H), 1.45-1.37 (m, 2H), 0.95 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 167.0, 162.0, 128.6, 127.1, 113.7, 55.4, 39.7, 31.8, 20.2, 13.8. These data were identical to those reported previously.10

2-(4-Methoxyphenyl)-2-oxo-N,N-dipropylacetamide (3ah) and 4-Methoxy-N,N-dipropyl- benzamide (4ah) (Table 1, run 7). A crude product, which was obtained from 1a (118.9 mg, 0.508 mmol), K2CO3 (139.7 mg, 1.01 mmol), 2h (205.0 µL, 1.50 mmol), and bibenzyl (48.0 mg, 0.263 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 6/1) to give 3ah (99.8 mg, 75%) as a yellow oil and 4ah (12.6 mg, 20%) as a yellow oil, respectively. Spectral data of 3ah: IR (neat) 1671, 1637, 1599 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.9 Hz, 2H), 6.96 (d, J = 8.9 Hz, 2H), 3.88 (s, 3H), 3.44 (t, J = 7.7 Hz, 2H), 3.12 (t, J = 7.7 Hz, 2H), 1.74-1.67 (m, 2H), 1.61-1.53 (m, 2H) 0.99 (t, J = 7.5 Hz, 3H), 0.78 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 190.3, 167.5, 164.6, 132.0, 126.4, 114.2, 55.6, 49.3, 45.7, 21.8, 20.6, 11.4, 11.0; EI-LRMS m/z 263 (M+), 135; EI-HRMS calcd. for C15H21NO3 263.15214, found 263.15184. Spectral data of 4ah: IR data; 1630 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.33-7.30 (m, 2H), 6.90-6.87 (m, 2H), 3.82 (s, 3H), 3.59-3.30 (br, 4H), 1.74-1.43 (br, 4H), 1.07-0.59 (br, 6H); 13C NMR (125 MHz, CDCl3) δ 171.7, 160.1, 129.6, 128.3, 113.6, 55.3, 50.9 (br), 46.5 (br), 21.9 (br), 20.6 (br), 11.2 (br); EI-LRMS m/z 235 (M+), 135; EI-HRMS calcd. for C14H20NO2 234.14940, found 234.14945

N-Benzyl-2-(4-methoxyphenyl)-N-methyl-2-oxoacetamide (3ai) (Table 1, run 8). A crude product, which was obtained from 1a (116.3 mg, 0.497 mmol), K2CO3 (139.2 mg, 1.01 mmol), 2i (195.0 µL, 1.51 mmol), and bibenzyl (45.6 mg, 0.250 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 4/1~1/2) followed by preparative thin-layer chromatography on silica gel (hexane/AcOEt = 3/1) to give 3ai (134.9 mg, 87%) as an colorless oil. Spectral data of 3ai: IR (neat) 1668, 1643, 1599 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.97-7.92 (m, 2H), 7.40-7.25 (m, 5H) 6.99-6.97 (m, 2H), 4.72 (s, 1.1H), 4.39 (s, 0.9H), 3.88 (m, 3H), 2.97 (s, 1.4H), 2.84 (s, 1.6H); 13C NMR (125 MHz, CDCl3) δ 190.2, 167.6, 167.4, 164.8, 135.9, 135.0, 132.2, 132.1, 128.8, 128.3, 128.1, 127.8, 126.8, 126.3, 126.1, 114.3, 55.6, 53.5, 49.7, 34.5, 31.3; EI-LRMS m/z 283 (M+), 135; EI-HRMS calcd. for C17H17NO3 283.12084, found 283.12021.

N-(2-tert-Butyldimethylsiloxyethyl)-2-(4-methoxyphenyl)-N-methyl-2-oxoacetamide (3aj) (Table 1, run 9). A crude product, which was obtained from 1a (118.7 mg, 0.507 mmol), K2CO3 (141.4 mg, 1.02 mmol), 2j (342 µL, 1.50 mmol), and bibenzyl (45.8 mg, 0.251mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 4/1~1/1) to give 3aj (124.3 mg, 70%) as a colorless oil. Spectral data of 3aj: IR (neat) 1672, 1646, 1600 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.93-7.89 (m, 2H), 6.96-6.93 (m, 2H), 3.90 (t, J = 5.3 Hz, 1H), 3.87 (s, 3H), 3.70 (t, J = 5.7 Hz, 1H), 3.63 (t, J = 5.3 Hz, 1H), 3.34 (t, J = 5.7 Hz, 1H), 3.15-3.02 (m, 3H), 0.90-0.83 (m, 9H), 0.09--0.03 (m, 6H); 13C NMR (125 MHz, CDCl3) δ 190.5, 167.7, 167.5, 164.7, 132.2, 132.1, 126.3, 126.1, 114.2, 61.6, 61.1, 55.6, 51.8, 49.3, 37.0, 33.4, 25.8, 25.8, 18.1; EI-LRMS: m/z 351 (M+), 336, 294, 216, 135; EI-HRMS calcd. for C18H29NO4Si 354.18658, found 351.18670. 4-Methoxy-N-phenylbenzamide (4ak) (Table 1, run 10). A crude product was obtained from 1a 10 P. Nordeman, L. R. Odell, M. Larhed, J. Org. Chem. 2012, 77, 11393-11398.

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(117.0 mg, 0.500 mmol), K2CO3 (138.9 mg, 1.00 mmol), 2k (140 µL, 1.54 mmol), and bibenzyl (48.8 mg, 0.268 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours. The yield of 4ak was determined by 1H NMR analysis of the crude product using 1,3,5-trimethoxybenzene (δ = 6.1 ppm in CDCl3, 3H) as an internal standard (55%). Analytically pure samples were obtained by recycle preparative thin-layer chromatography on silica gel (hexane/AcOEt = 5/1).1H and 13C NMR data of 4ak: 1H NMR (500 MHz, CDCl3) δ 7.85 (d, J = 8.9 Hz, 2H), 7.70 (brs, 1H), 7.63 (d, J = 7.4 Hz), 7.39-7.36 (m, 2H), 7.16-7.13 (m, 1H), 6.99 (d, J = 8.9 Hz, 2H), 3.88 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 165.2, 152.4, 138.1, 129.0, 128.9, 127.1, 124.3, 120.1, 113.9, 55.5. These data were identical to those reported previously.11

1-(3-Methoxyphenyl)-2-morpholinoethane-1,2-dione (3ba) and N-(3-Methoxybenzoyl)- morpholine (4ba) (Table 2, run 1). A crude product, which was obtained from 1b (117.2 mg, 0.502 mmol), K2CO3 (138.9 mg, 1.01 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (48.8 mg, 0.268 mmol) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/1) to give 3ba (104.6 mg, 84%) as a colorless solid and4ba (15.6 mg, 14%) as a colorless oil, respectively. 1H and 13C NMR data of 3ba: 1H NMR (500 MHz, CDCl3) δ 7.48-7.46 (m, 2H), 7.40 (dd, J = 8.0, 8.0 Hz, 1H), 7.17 (m, 1H), 3.83 (s, 3 H), 3.78-3.74 (br, 4H), 3.62 (t, J = 4.9 Hz, 2H), 3.34 (t, J = 4.87, 2 H); 13C NMR (125 MHz, CDCl3) δ 191.0, 165.3, 160.0, 134.2, 130.1, 122.7, 121.7, 112.6, 66.6, 66.5, 55.4, 46.1, 41.5. These data were identical to those reported previously.12 1H and 13C NMR data of 4ba: 1H NMR (500 MHz, CDCl3) δ 7.31 (m, 1H), 6.96-6.94 (m, 3H). 3.81 (s, 3H), 3.87-3.26 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 170.2, 159.7, 136.6, 129.7, 119.1, 115.6, 112.5, 66.9, 55.4, 48.2 (br), 42.5 (br). These data were identical to those reported previously.5

1-(2-Methoxyphenyl)-2-morpholinoethane-1,2-dione (3ca) and N-(2-Methoxybenzoyl)- morpholine (4ca) (Table 2, run 2). A crude product, which was obtained from 1c (118.1 mg, 0.502 mmol), K2CO3 (137.7 mg, 1.01 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (48.1 mg, 0.268 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 4/1~1/2) to give an inseparable mixture of 3ca and 4ca (97.4 mg, 3ca: 29%, 4ca: 55%) as a yellow oil. Analytically pure samples were obtained by recycle preparative thin-layer chromatography on silica gel (hexane/AcOEt = 1/1). 1H and 13C NMR data of 3ca: 1H NMR (500 MHz, CDCl3) δ 7.93 (dd, J = 7.9, 1.7 Hz, 1H), 7.58 (ddd, J = 8.7, 8.2, 1.7 Hz, 1H), 7.09 (dd, J = 8.2, 7.9 Hz, 1H), 7.00 (d, J = 8.7 Hz, 1H), 3.91 (s, 3H), 3.79 (t, J = 4.6 Hz, 2H), 3.72-3.69 (m, 4H), 3.40 (t, J = 4.6 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 190.2, 167.4, 160.1, 136.2, 131.1, 123.5, 121.5, 112.2, 66.5, 66.3, 56.2, 45.9, 41.4. These data were identical to those reported previously.2 1H and 13C NMR data of 4ca: 1H NMR (500 MHz, CDCl3) δ 7.36 (m, 1H), 7.24 (m, 1H), 7.00 (m, 1H), 6.91 (d, J = 8.6 Hz, 1H), 3.83 (s, 3H), 3.90-3.72 (m, 4H), 3.63-3.56 (m, 2H), 3.29-3.22 (m, 2H); 13C NMR (125 MHz, CDCl3) 167.8, 155.2, 130.6, 128.0, 125.2, 121.0, 110.8, 66.9, 66.8, 55.5, 47.2, 42.1. These data were identical to those reported previously.7

1-(3,5-Dimethylphenyl)-2-morpholinoethane-1,2-dione (3da) and N-(3,5-Dimethylbenzoyl)- morpholine (4da) (Table 2, run 3). A crude product, which was obtained from 1d (120.0 mg, 0.517 mmol), K2CO3 (140.9 mg, 1.02 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (51.8 mg,

11 E. Racine, F. Monnier, J. P. Vors, M. Taillefer, Org. Lett. 2011, 13, 2818-2821. 12 W. Wei, Y. Shao, H. Hu, F. Zhang, C. Zhang, Y. Xu, X. Wan, J. Org. Chem. 2012, 77, 7157-7165.

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0.284 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/2) to give 3da (97.2 mg, 76%) as a white solid and 4da (7.9 mg, 7%) as a yellow amorphous solid, respectively. Spectral data of 3da: mp 101 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1677, 1643 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.54 (s, 2H), 7.28 (s, 1H), 3.80-3.76 (m, 4H), 3.64 (t, J = 4.9 Hz, 2H), 3.35 (t, J = 4.9 Hz, 2H), 2.37 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 191.6, 165.7, 138.9, 136.7, 133.0, 127.3, 66.7, 66.6, 46.2, 41.5, 21.1; EI-LRMS m/z 247 (M+), 133; EI-HRMS calcd. for C14H17NO3 247.12084, found 247.12042. 1H and 13C NMR data of 4da: 1H NMR (500 MHz, CDCl3) δ 7.04 (s, 1H), 6.99 (s, 2H), 4.01-3.24 (br, 8H), 2.33 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 170.8, 138.3, 135.3, 131.3, 124.6, 66.9, 48.2, 42.5, 21.2. These data were identical to those reported previously.3

1-Morpholino-2-(3,4,5-trimethoxyphenyl)ethane-1,2-dione (3ea) and N-(3,4,5-Trimethoxy- benzoyl)morpholine (4ea) (Table 2, run 4). A crude product, which was obtained from 1e (146.9 mg, 0.496 mmol), K2CO3 (140.4 mg, 1.02 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (48.0 mg, 0.263 mmol) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/5) to give 3ea (132.6 mg, 86%) as a colorless solid and 4ea (4.8 mg, 4%) as a yellow oil, respectively. Spectral data of 3ea: mp 133 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1673, 1644 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.17 (s, 2H), 3.91 (s, 3H), 3.88 (s, 3H), 3.75 (s, 4H), 3.63 (t, J = 4.9 Hz, 2H), 3.35 (t, J = 4.9 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 189.9, 165.2, 153.3, 144.1, 127.9, 106.8, 66.7, 66.6, 60.9, 56.3, 46.2, 41.6; EI-LRMS m/z 309 (M+), 195; EI-HRMS calcd. for C15H19NO6 309.12124, found 309.12109. 1H NMR data of 4ea: 1H NMR (500 MHz, CDCl3) δ 6.61 (s, 2H), 3.86 (s, 6H), 3.84 (s, 3H), 3.85-3.47 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 170.1, 153.3, 139.2, 130.6, 104.3, 66.9, 60.9, 56.2, 48.3 (br), 42.7 (br). These data were identical to those reported previously.13

1-Morpholino-2-phenylethane-1,2-dione (3fa) and N-Benzoylmorpholine (4fa) (Tbale 2, run 5). A crude product, which was obtained from 1f (104.2 mg, 0.511 mmol), K2CO3 (141.3 mg, 1.02 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (46.6 mg, 0.256 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/2) to give 3fa (77.7 mg, 69%) as a colorless solid and 4fa (21.1 mg, 22%) as a yellow oil, respectively. 1H and 13C NMR data of 3fa: 1H NMR (500 MHz, CDCl3) δ 7.97-7.95 (m, 2H), 7.66 (m, 1H), 7.54-7.51 (m, 2H), 3.82-3.78 (m, 4H), 3.65 (t, J = 4.7 Hz, 2H), 3.38 (t, J = 4.7 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 191.0, 165.2, 134.7, 132.7, 129.4, 128.9, 66.4, 46.0, 41.3. These data were identical to those reported previously.2 1H and 13C NMR data of 4fa: 1H NMR (500 MHz, CDCl3) δ 7.42-7.41 (m, 5H), 4.05-3.20 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 170.4, 135.3, 129.9, 128.6, 127.1, 66.9, 48.2 (br), 42.5 (br). These data were identical to those reported previously.7

1-(4-Chlorophenyl)-2-morpholinoethane-1,2-dione (3ga) and N-(4-Chlorobenzoyl)morpholine (4ga) (Table 2, run 6). A crude product, which was obtained from 1g (120.2 mg, 0.504 mmol), K2CO3 (138.8 mg, 1.00 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (48.0 mg, 0.263 mmol, internal standard for GC analysis), DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/2) to give 3ga (82.7 mg, 0.326 mmol, 65%) as a colorless solid and 4ga (30.6 mg, 0.136 mmol, 27%) as a colorless solid, respectively. 1H and

13 G. R. Pettit, M. P. Grealish, D. L. Herald, M. R. Boyd, E. Hamel, R. K. Pettit, J. Med. Chem. 2000, 43, 2731-2737.

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13C NMR data of 3ga: 1H NMR (500 MHz, CDCl3) δ 7.91-7.88 (m, 2H), 7.50-7.47 (m, 2H), 3.79-3.75 (m, 4H), 3.65-3.63 (m, 2H), 3.38-3.36 (m, 2H); 13C NMR(125 MHz, CDCl3) δ 189.6, 164.8, 141.5, 131.4, 131.0, 129.4, 66.7, 66.6, 46.2, 41.6. These data were identical to those reported previously.2 1H and 13C NMR data of 4ga: 1H NMR (500 MHz, CDCl3) δ 7.41-7.35 (m, 4H), 4.04-3.15 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 169.3, 136.0, 133.6, 128.8, 128.6, 66.8, 48.2 (br), 42.6 (br). These data were identical to those reported previously.14

1-(4-Methoxycarbonylphenyl)-2-morpholinoethane-1,2-dione (3ha) and N-(4-Methoxy- carbonylbenzoyl)morpholine (4ha) (Table 2, run 7). A crude product, which was obtained from 1h (132.5 mg, 0.506 mmol), K2CO3 (140.8 mg, 1.02 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (47.2 mg, 0.259 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 1/1~1/2) to give 3ha (63.9 mg, 46%) as a yellowish solid and 4ha (53.5 mg, 42%) as a yellow solid, respectively. Spectral data of 3ha: mp 139 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1724, 1685, 1646 cm-1; 1H NMR (500 MHz, CDCl3) δ 8.16 (d, J = 8.6 Hz, 2H), 8.02 (d, J = 8.6 Hz, 2H), 3.95 (s, 3H), 3.79 (brs, 4H), 3.66 (t, J = 4.9 Hz, 2H), 3.38 (t, J = 4.6 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 190.2, 165.8, 164.8, 136.1, 135.3, 130.1, 129.5, 66.7, 66.6, 52.6, 46.2, 41.7; EI-LRMS m/z 277 (M+), 246, 163, 135; EI-HRMS calcd. for C14H15NO5 277.09502, found 277.09458. 1H and 13C NMR data of 4ha: 1H NMR (500 MHz, CDCl3) δ 8.08 (d, J = 8.0 Hz, 2H), 7.46 (d, J = 8.0 Hz, 2H), 3.92 (s, 3H), 3.88-3.21 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 169.3, 166.2, 139.5, 131.3, 129.9, 127.0, 66.8, 52.3, 48.0, 42.5. These data were identical to those reported previously.15

1-(2,2-Dimethyl-4-oxo-4H-benzo[d][1,3]dioxin-6-yl)-2-morpholinoethane-1,2-dione (3ia) and 2,2-Dimethyl-6-(morpholine-4-carbonyl)-4H-benzo[d][1,3]dioxin-4-one (4ia) (Table 2, run 8). A crude product, which was obtained from 1i (154.4 mg, 0.507 mmol), K2CO3 (142.0 mg, 1.03 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (51.5 mg, 0.283 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/5) to give 3ia (70.6 mg, 44%) as a colorless solid and 4ia (76.8 mg, 52%) as a colorless solid, respectively. Spectral data of 3ia: mp 127 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1747, 1682, 1644, 1612; 1H NMR (500 MHz, CDCl3) δ 8.52 (d, J = 2.3 Hz, 1H), 8.21 (dd, J = 8.6, 2.3 Hz, 1H), 7.10 (d, J = 8.6 Hz, 1H), 3.82-3.77 (m, 4H), 3.68 (t, J = 4.9 Hz, 2H), 3.41 (t, J = 4.9 Hz, 2H), 1.76 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 188.4, 164.6, 160.6, 159.6, 136.9, 132.8, 128.0, 118.4, 113.4, 107.4, 66.7, 66.6, 46.3, 41.8, 25.9; EI-LRMS m/z 319 (M+), 205; EI-HRMS calcd. for C16H17NO6 319.10559, found 319.10511. Spectral data of 4ia: mp 124 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1743, 1632; 1H NMR (500 MHz, CDCl3) δ 7.98 (s, 1 H), 7.65 (d, J = 8.5 Hz, 1H), 7.12 (d, J = 8.5 Hz, 1H), 3.99-3.22 (br, 8H), 1.72 (s, 6H); 13C NMR (125 MHz, CDCl3) δ 168.5, 160.2, 157.0, 135.7, 129.6, 128.5, 117.8, 113.0, 106.8, 66.7, 48.3 (br), 42.8 (br), 25.7; EI-LRMS m/z 291 (M+), 205; EI-HRMS calcd. for C15H17NO5 291.11067, found 291.11070

1-Morpholino-2-(thiophen-3-yl)ethane-1,2-dione (3ja) and Morpholino(thiophen-3-yl)- methanone (4ja) (Table 2, run 9). A crude product, which was obtained from 1j (104.7 mg, 0.498 mmol), K2CO3 (138.3 mg, 1.00 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (48.6 mg,

14 J. Zhu, Y. Zhang, F. Shi, Y. Deng, Tetrahedron Lett. 2012, 53, 3178-3180. 15 R. Cadoni, A. Porcheddu, G. Giacomelli, L. D. Luca, Org. Lett. 2012, 14, 5014-5017.

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0.267 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/2) to give 3ja (94.1 mg, 84%) as a colorless oil and 4ja (16.0 mg, 16%) as a colorless oil, respectively. Spectral data of 3ja: IR (film, CHCl3) 1672, 1642 cm-1; 1H NMR (500 MHz, CDCl3) δ 8.23 (dd, J = 2.9, 1.2 Hz, 1H), 7.57 (dd, J = 5.2, 1.2 Hz, 1H), 7.37 (dd, J = 5.2, 2.9 Hz, 1H), 3.77-3.72 (m, 4H), 3.65 (t, J = 4.9 Hz, 2H), 3.42 (t, J = 4.9 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 184.3, 165.1, 138.4, 136.7, 127.3, 126.8, 66.7, 66.6, 46.3, 41.7; EI-LRMS m/z 225 (M+), 111; EI-HRMS calcd. for C10H11NO3S 225.04596, found 225.04567. 1H and 13C NMR data of 4ja: 1H NMR (500 MHz, CDCl3) δ 7.52 (dd, J = 3.0, 1.2 Hz, 1H), 7.34 (dd, J = 5.0, 3.0 Hz, 1H), 7.17 (dd, J = 5.0, 1.2 Hz, 1H), 4.00-3.30 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 165.7, 135.9, 126.9, 126.6, 126.1, 66.8, 47.9 (br), 42.6 (br). These data were identical to those reported previously.13

1-(1-Methyl-1H-indol-3-yl)-2-morpholinoethane-1,2-dione (3ka) and (1-Methyl-1H-indol-3-yl) (morpholino)methanone (4ka) (Table 2, run 10). A crude product, which was obtained from 1k (129.9 mg, 0.505 mmol), K2CO3 (141.8 mg, 1.03 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (50.4 mg, 0.277 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 4/1~1/2) to give 3ka (129.7 mg, 94%) and colorless solid 4ka (6.8 mg, 6%) as a yellowish solid. Spectral data of 3ka: mp 157 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1662, 1642, 1607 cm-1; 1H NMR (500 MHz, CDCl3) δ 8.21 (d, J = 1.2 Hz, 1H), 7.82 (dd, J = 8.6, 1.2 Hz, 1H), 7.34 (d, J = 8.6 Hz, 1H), 7.12 (d, J = 2.9 Hz, 1H), 6.58 (d, J = 2.9 Hz, 1H), 3.78 (s, 3H), 3.78 (s, 3H), 3.60 (t, J = 4.9 Hz, 2H), 3.36 (t, J = 4.9 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 191.5, 166.4, 139.9, 131.0, 128.0, 125.3, 124.8, 122.1, 109.8, 103.3, 66.6, 66.5, 46.2, 41.3, 32.9; EI-LRMS m/z 272 (M+), 158; EI-HRMS calcd. for C15H16N2O3 272.11609, found 272.11587. Spectral data of 4ka: mp 132 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1621 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.70 (s, 1H), 7.32-7.27 (m, 2H), 7.08 (d, J = 3.2 Hz, 1H), 6.50 (d, J = 3.2 Hz, 1H), 3.76 (s, 3H), 3.79-3.55 (br, 8H); 13C NMR δ 171.7, 137.1, 129.9, 127.7, 126.0, 120.9, 120.4, 109.0, 101.5, 66.8, 48.2, 43.0 (br), 32.8 (br); EI-LRMS m/z 244 (M+), 158; EI-HRMS calcd. for C14H16N2O2 244.12118, found 244.12010.

1-Morpholino-2-(quinolin-6-yl)ethane-1,2-dione (3la) and Morpholino(quinolin-6-yl) methanone (4la) (Table 2, run 11). A crude product, which was obtained from 1l (128.4 mg, 0.503 mmol), K2CO3 (138.9 mg, 1.01 mmol), 2a (130.0 µL, 1.49 mmol), and bibenzyl (48.8 mg, 0.268 mmol, internal standard for GC analysis) in DMF at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 4/1~1/2) to give 3la (108.9 mg, 0.403 mmol, 80%) as a colorless solid and 4la (20.3 mg, 0.167 mmol, 17%) as a colorless solid, respectively. Spectral data of 3la: mp 127 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1680, 1645 cm-1; 1H NMR (500 MHz, CDCl3) δ 9.18 (dd, J = 4.2, 1.4 Hz, 1H), 8.45 (d, J = 1.7 Hz, 1H), 8.27 (dd, J = 8.2, 1.4 Hz, 1H), 8.23 (dd, J = 8.6, 1.7 Hz, 1H), 8.17 (d, J = 8.6 Hz, 1H), 7.49 (dd, J = 8.2, 4.2 Hz, 1H), 3.81 (s, 4H), 3.65 (t, J = 4.9 Hz, 2H), 3.41 (t, J = 4.9 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ 190.3, 165.0, 153.4, 150.7, 137.7, 132.6, 130.7 (2C), 127.4 (2C), 122.3, 66.7, 66.6, 46.3, 41.7; EI-LRMS m/z 270 (M+), 156; EI-HRMS calcd. for C15H14N2O3 270.10044, found 270.10024. Spectral data of 4la: mp 121 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1633 cm-1; 1H NMR (500 MHz, CDCl3) δ 8.99 (brs, 1H), 8.21 (d, J = 8.0 Hz, 1H), 8.16 (d, J = 8.6 Hz, 1H), 7.93 (s, 1H), 7.73 (dd, J = 8.6, 1.7 Hz, 1H), 7.48 (m, 1H), 4.00-3.34 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 169.7, 151.6, 148.4, 136.5, 133.4, 130.1 (2C), 127.8, 127.1, 122.0, 66.9, 48.3 (br), 42.7 (br); ESI-LRMS m/z 265.09 ([M+Na]+); ESI-HRMS calcd. for C14H14O2N2Na 265.09475, found 265.09476.

~ S10 ~

Page 11: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

1-(4-Benzoylpiperazin-1-yl)-2-(naphthalen-2-yl)ethane-1,2-dione (3ml) and [4-(2-Naphthoyl) piperazin-1-yl](phenyl)methanone (4ml) (Scheme 3). A crude product, which was obtained from 1m (131.7 mg, 0.518 mmol), K2CO3 (138.2 mg, 1.00 mmol), 2l (285.6 mg, 1.50 mmol), and bibenzyl (48.7 mg, 0.267 mmol, internal standard for GC analysis) in DMF (3 mL) at 80 °C for 24 hours, was purified by flash column chromatography on silica gel (hexane/AcOEt = 4/1~2/1) to give 3ml (159.7 mg, 83%) as a colorless solid and 4ml (27.3 mg, 15%) as a colorless slid, respectively. Spectral data of 3ml: mp 144 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1673, 1638 cm-1; 1H NMR (500 MHz, CDCl3) δ 8.45 (s, 1H), 7.99-7.87 (m, 4H), 7.64 (m, 1H) 7.57 (m, 1H), 7.40 (s, 5H), 4.20-3.03 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 191.0, 170.6, 165.6, 136.4, 134.8, 133.1, 132.3, 130.2, 129.8, 129.6, 129.2, 128.6, 127.9, 127.2, 126.9, 123.4, 47.2 (br), 45.9 (br), 42.0 (br), 41.4 (br); EI-LRMS m/z 372 (M+), 189, 155; EI-HRMS calcd. for C23H20N2O3 372.14739, found 372.14628. Spectral data of 4mk: mp 184 °C (recrystallized from CHCl3/hexane); IR (film, CHCl3) 1629 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.92-7.87 (m, 4H), 7.55-7.42 (m, 8H), 4.20-3.14 (br, 8H); 13C NMR (125 MHz, CDCl3) δ 170.6, 135.1, 133.7, 132.6, 132.3, 130.1, 128.6, 128.5, 128.4, 127.8, 127.3, 127.2, 127.1, 127.0, 126.8, 124.0, 47.7 (br), 42.5 (br); EI-LRMS m/z 344 (M+), 189, 155; EI-HRMS calcd. for C22H20N2O2 344.15248, found 344.15248. Large-scale reactions. For the reaction of 1a and 2a (Scheme 4, Eq 1). A mixture of 1a (2.34 g, 10.0 mmol), K2CO3 (2.78 g, 20.1 mmol), 2a (2.6 mL, 30.1 mmol) and 2 sheets of SAPd in DMF (10 mL) was stirred at 80 °C for 24 hours. After the usual work-up, the crude product was purified by flash column chromatography on silica gel (hexane/AcOEt = 2/1~1/1) to give 3aa (2.13 g, 85%) and 4aa (105.2 mg, 5%), respectively

For the reaction of 1m and 2l (Scheme 4, Eq 2). A mixture of 1m (2.54 g, 10.0 mmol), K2CO3 (2.77 g, 20.0 mmol), 2l (5.71 g, 30.0 mmol) and 2 sheets of SAPd in DMF (10 mL) was stirred at 80 °C for 24 hours. After the usual work-up, the crude product was purified by flash column chromatography on silica gel (hexane/AcOEt = 1/1~1/2) to give 3ml (3.06 g, 82%) and 4mk (569.4 mg, 17%), respectively

~ S11 ~

Page 12: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

Examination of reusability of SAPd (Table 3)

After the solution of 1a in DMF in the presence of K2CO3 and SAPd was heated at 80 °C for 2 hours, SAPd was removed and reused to the next reaction without purification. The yields shown in Table 3 were calculated by GC analysis using bibenzyl as an internal standard.

Run 1 cycle 1

cycle 2

cycle 3

cycle 4

cycle 5

1a (mg) 117.3 117.0 118.3 117.5 117.3 2a (µL) 130.0 130.0 130.0 130.0 130.0 bibenzyl (mg) 47.8 47.8 47.9 49.5 48.8 K2CO3 (mg) 139.0 138.0 139.5 138.3 138.2

yields (%) 3aa 88 90 90 90 89 4aa 7 7 8 8 6

Run 2 cycle 1

cycle 2

cycle 3

cycle 4

cycle 5

1a (mg) 117.8 117.5 116.7 117.2 117.1 2a (µL) 130.0 130.0 130.0 130.0 130.0 bibenzyl (mg) 47.0 46.7 50.6 47.9 48.7 K2CO3 (mg) 138.4 138.3 139.1 138.3 138.2

yields (%) 3aa 89 90 91 93 91 4aa 7 8 7 7 7

Run 3 cycle 1

cycle 2

cycle 3

cycle 4

cycle 5

1a (mg) 117.5 117.8 117.5 117.5 117.7 2a (µL) 130.0 130.0 130.0 130.0 130.0 bibenzyl (mg) 45.7 51.2 48.3 49.1 50.3 K2CO3 (mg) 139.1 138.7 138.5 138.4 138.7

yields (%) 3aa 84 84 92 90 89 4aa 6 8 6 8 7

~ S12 ~

Page 13: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

Data of ICP-MS analysis

Amount of palladium in the reaction mixture of 1a and 2aa), and in SAPd

Amount of leached Pd (µg) in the reaction mixtureb) Immobilized Pd on SAPd (µg)

cycle 1 cycle 2 cycle 3 cycle 4 cycle 5 after use

before use

leached Pd (µg) (mol%)c)

run 1 10 (0.019)

11 (0.021)

22 (0.041)

15 (0.028)

5 (0.009) 87 408

run 2 62 (0.116)

63 (0.118)

35 (0.066)

46 (0.086)

28 (0.053) 40 338

run 3 96 (0.180)

78 (0.146)

29 (0.054)

28 (0.052)

36 (0.067) 136 329

average (µg) 56 50 28 30 23 88 358

standard deviationc) 43 35 7 16 16 48 43

a) Reaction conditions: 1a (0.5 mmol), 2a (3 equiv), K2CO3 (2 equive), bibenzyl (0.5 equiv, internal standard) DMF (3 mL), 80 °C, 24 hours b) The reaction mixture was acidified and subjected directly to ICP-MS. c) Value in parentheses indicats the loading of Pd catalyst (mol%). d) The standard deviation was calculated from three sets of samples.

~ S13 ~

Page 14: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00

2.00 2.00 2.00 2.00

2.06 2.06 2.06 2.06

3.15 3.15 3.15 3.154.12 4.12 4.12 4.12

2.07 2.07 2.07 2.07

2.04 2.04 2.04 2.04

7.938 7.938 7.938 7.9387.921 7.921 7.921 7.921

7.260 7.260 7.260 7.260

6.991 6.991 6.991 6.9916.974 6.974 6.974 6.974

3.893 3.893 3.893 3.8933.799 3.799 3.799 3.7993.784 3.784 3.784 3.7843.781 3.781 3.781 3.7813.767 3.767 3.767 3.7673.657 3.657 3.657 3.6573.648 3.648 3.648 3.6483.638 3.638 3.638 3.6383.389 3.389 3.389 3.3893.379 3.379 3.379 3.3793.370 3.370 3.370 3.370

MeO

ON

O

O

3aa

CD

Cl 3

, 500

MH

z

~ S14 ~

Page 15: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

189.800 189.800 189.800 189.800

165.773 165.773 165.773 165.773165.001 165.001 165.001 165.001

132.141 132.141 132.141 132.141

126.113 126.113 126.113 126.113

114.390 114.390 114.390 114.390

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.765 66.765 66.765 66.765 66.670 66.670 66.670 66.670

55.653 55.653 55.653 55.653

46.277 46.277 46.277 46.277

41.527 41.527 41.527 41.527

MeO

O

N

O

O

3aa

CD

Cl 3

, 125

MH

z

~ S15 ~

Page 16: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00

2.00 2.00 2.00 2.00

2.02 2.02 2.02 2.02

11.36 11.36 11.36 11.36

7.384 7.384 7.384 7.3847.378 7.378 7.378 7.3787.373 7.373 7.373 7.3737.364 7.364 7.364 7.3647.361 7.361 7.361 7.3617.260 7.260 7.260 7.2606.912 6.912 6.912 6.9126.907 6.907 6.907 6.9076.903 6.903 6.903 6.9036.894 6.894 6.894 6.8946.889 6.889 6.889 6.889

3.812 3.812 3.812 3.8123.676 3.676 3.676 3.676

MeO

O

N

O

4aa

CD

Cl 3

, 50

0 M

Hz

~ S16 ~

Page 17: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

170.371 170.371 170.371 170.371

160.842 160.842 160.842 160.842

129.156 129.156 129.156 129.156127.267 127.267 127.267 127.267

113.732 113.732 113.732 113.732

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.870 66.870 66.870 66.870

55.319 55.319 55.319 55.319

48.223 48.223 48.223 48.223

43.005 43.005 43.005 43.005

MeO

O

N

O

4aa

CD

Cl 3

, 12

5 M

Hz

~ S17 ~

Page 18: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

2.09 2.09 2.09 2.09

3.15 3.15 3.15 3.15

2.09 2.09 2.09 2.09

2.08 2.08 2.08 2.08

4.16 4.16 4.16 4.16

7.926 7.926 7.926 7.9267.921 7.921 7.921 7.9217.917 7.917 7.917 7.9177.907 7.907 7.907 7.9077.904 7.904 7.904 7.9047.898 7.898 7.898 7.8987.260 7.260 7.260 7.2606.934 6.934 6.934 6.9346.928 6.928 6.928 6.9286.924 6.924 6.924 6.9246.914 6.914 6.914 6.9146.910 6.910 6.910 6.9106.905 6.905 6.905 6.905

3.831 3.831 3.831 3.8313.601 3.601 3.601 3.6013.587 3.587 3.587 3.5873.574 3.574 3.574 3.5743.376 3.376 3.376 3.3763.363 3.363 3.363 3.3633.349 3.349 3.349 3.349

1.930 1.930 1.930 1.9301.918 1.918 1.918 1.9181.904 1.904 1.904 1.9041.898 1.898 1.898 1.8981.894 1.894 1.894 1.8941.889 1.889 1.889 1.8891.884 1.884 1.884 1.8841.880 1.880 1.880 1.8801.866 1.866 1.866 1.8661.854 1.854 1.854 1.854

MeO

O

N

O

3ab

CD

Cl 3

, 500

MH

z

~ S18 ~

Page 19: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

190.191 190.191 190.191 190.191

165.172 165.172 165.172 165.172164.610 164.610 164.610 164.610

132.170 132.170 132.170 132.170

125.769 125.769 125.769 125.769

114.104 114.104 114.104 114.104

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

55.491 55.491 55.491 55.491

46.535 46.535 46.535 46.535 45.018 45.018 45.018 45.018

25.751 25.751 25.751 25.751 23.881 23.881 23.881 23.881

MeO

O

N

O

3ab

CD

Cl 3

, 125

MH

z

~ S19 ~

Page 20: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

1.98 1.98 1.98 1.98

3.18 3.18 3.18 3.18

4.49 4.49 4.49 4.49

4.21 4.21 4.21 4.21

7.521 7.521 7.521 7.5217.504 7.504 7.504 7.5047.260 7.260 7.260 7.260

6.902 6.902 6.902 6.9026.884 6.884 6.884 6.884

3.828 3.828 3.828 3.8283.643 3.643 3.643 3.6433.630 3.630 3.630 3.6303.616 3.616 3.616 3.6163.487 3.487 3.487 3.4873.474 3.474 3.474 3.4743.461 3.461 3.461 3.461

1.975 1.975 1.975 1.9751.961 1.961 1.961 1.9611.947 1.947 1.947 1.9471.935 1.935 1.935 1.9351.921 1.921 1.921 1.9211.888 1.888 1.888 1.8881.876 1.876 1.876 1.8761.863 1.863 1.863 1.8631.850 1.850 1.850 1.850

MeO

O

N

4ab

CD

Cl 3

, 500

MH

z

~ S20 ~

Page 21: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

169.417 169.417 169.417 169.417

160.737 160.737 160.737 160.737

129.404 129.404 129.404 129.404129.127 129.127 129.127 129.127

113.370 113.370 113.370 113.370

77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

55.300 55.300 55.300 55.300

49.778 49.778 49.778 49.778 46.306 46.306 46.306 46.306

26.485 26.485 26.485 26.485 24.434 24.434 24.434 24.434

MeO

O

N

4ab

CD

Cl 3

, 125

MH

z

~ S21 ~

Page 22: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

2.05 2.05 2.05 2.05

3.15 3.15 3.15 3.152.10 2.10 2.10 2.10

2.08 2.08 2.08 2.08

4.10 4.10 4.10 4.10

2.06 2.06 2.06 2.06

7.891 7.891 7.891 7.8917.885 7.885 7.885 7.8857.882 7.882 7.882 7.8827.872 7.872 7.872 7.8727.868 7.868 7.868 7.8687.862 7.862 7.862 7.8627.260 7.260 7.260 7.2606.955 6.955 6.955 6.9556.950 6.950 6.950 6.9506.945 6.945 6.945 6.9456.936 6.936 6.936 6.9366.931 6.931 6.931 6.9316.926 6.926 6.926 6.926

3.848 3.848 3.848 3.8483.665 3.665 3.665 3.6653.654 3.654 3.654 3.6543.644 3.644 3.644 3.6443.260 3.260 3.260 3.2603.248 3.248 3.248 3.2483.238 3.238 3.238 3.238

1.655 1.655 1.655 1.6551.649 1.649 1.649 1.6491.644 1.644 1.644 1.6441.511 1.511 1.511 1.5111.499 1.499 1.499 1.4991.491 1.491 1.491 1.491

MeO

O

N

O

3ac

CD

Cl 3

, 500

MH

z

~ S22 ~

Page 23: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

190.592 190.592 190.592 190.592

165.659 165.659 165.659 165.659164.657 164.657 164.657 164.657

131.864 131.864 131.864 131.864

126.189 126.189 126.189 126.189

114.190 114.190 114.190 114.190

77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

55.520 55.520 55.520 55.520

46.926 46.926 46.926 46.926

41.928 41.928 41.928 41.928

26.104 26.104 26.104 26.104 25.340 25.340 25.340 25.340 24.263 24.263 24.263 24.263

MeO

O

N

O

3ac

CD

Cl 3

, 125

MH

z

~ S23 ~

Page 24: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

2.02 2.02 2.02 2.02

7.32 7.32 7.32 7.32

6.30 6.30 6.30 6.30

7.369 7.369 7.369 7.3697.352 7.352 7.352 7.3527.260 7.260 7.260 7.260

6.902 6.902 6.902 6.9026.884 6.884 6.884 6.884

3.820 3.820 3.820 3.8203.656 3.656 3.656 3.656

3.408 3.408 3.408 3.408

1.665 1.665 1.665 1.6651.590 1.590 1.590 1.590

MeO

O

N

4ac

CD

Cl 3

, 500

MH

z

~ S24 ~

Page 25: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

170.275 170.275 170.275 170.275

160.451 160.451 160.451 160.451

128.812 128.812 128.812 128.812128.555 128.555 128.555 128.555

113.579 113.579 113.579 113.579

77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

55.291 55.291 55.291 55.291

48.995 48.995 48.995 48.995

43.368 43.368 43.368 43.368

26.361 26.361 26.361 26.361 25.674 25.674 25.674 25.674 24.616 24.616 24.616 24.616

MeO

O

N

4ac

CD

Cl 3

, 125

MH

z

~ S25 ~

Page 26: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

2.02 2.02 2.02 2.02

5.63 5.63 5.63 5.63

1.98 1.98 1.98 1.98

2.01 2.01 2.01 2.012.08 2.08 2.08 2.08

3.11 3.11 3.11 3.11

7.878 7.878 7.878 7.8787.873 7.873 7.873 7.8737.868 7.868 7.868 7.8687.859 7.859 7.859 7.8597.854 7.854 7.854 7.8547.849 7.849 7.849 7.8497.260 7.260 7.260 7.2606.954 6.954 6.954 6.9546.950 6.950 6.950 6.9506.945 6.945 6.945 6.9456.935 6.935 6.935 6.9356.931 6.931 6.931 6.9316.926 6.926 6.926 6.926

3.846 3.846 3.846 3.8463.829 3.829 3.829 3.8293.817 3.817 3.817 3.8173.436 3.436 3.436 3.4363.427 3.427 3.427 3.4273.417 3.417 3.417 3.417

2.648 2.648 2.648 2.6482.638 2.638 2.638 2.6382.628 2.628 2.628 2.6282.526 2.526 2.526 2.5262.515 2.515 2.515 2.5152.505 2.505 2.505 2.5052.377 2.377 2.377 2.377

MeO

ON

O

N

3ad

CD

Cl 3

, 500

MH

z

Me

~ S26 ~

Page 27: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

189.838 189.838 189.838 189.838

165.592 165.592 165.592 165.592164.934 164.934 164.934 164.934

132.046 132.046 132.046 132.046

125.827 125.827 125.827 125.827

114.333 114.333 114.333 114.333

77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

55.577 55.577 55.577 55.577 54.423 54.423 54.423 54.423 54.013 54.013 54.013 54.013

45.371 45.371 45.371 45.371 45.008 45.008 45.008 45.008 40.325 40.325 40.325 40.325

MeO

ON

O

N

3ad

CD

Cl 3

, 125

MH

z

Me

~ S27 ~

Page 28: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

2.03 2.03 2.03 2.03

7.00 7.00 7.00 7.00

7.16 7.16 7.16 7.16

7.388 7.388 7.388 7.3887.371 7.371 7.371 7.3717.260 7.260 7.260 7.260

6.915 6.915 6.915 6.9156.898 6.898 6.898 6.898

3.831 3.831 3.831 3.831

3.633 3.633 3.633 3.633

2.412 2.412 2.412 2.4122.319 2.319 2.319 2.319

MeO

O

N

N

4ad

CD

Cl 3

, 500

MH

z

Me

~ S28 ~

Page 29: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

170.313 170.313 170.313 170.313

160.899 160.899 160.899 160.899

129.146 129.146 129.146 129.146128.173 128.173 128.173 128.173

113.808 113.808 113.808 113.808

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

55.367 55.367 55.367 55.367 55.348 55.348 55.348 55.348 55.148 55.148 55.148 55.148

46.020 46.020 46.020 46.020

MeO

O

N

N

4ad

CD

Cl 3

, 125

MH

z

Me

~ S29 ~

Page 30: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

2.07 2.07 2.07 2.07

4.21 4.21 4.21 4.21 3.15 3.15 3.15 3.152.05 2.05 2.05 2.05

2.07 2.07 2.07 2.07

2.24 2.24 2.24 2.242.07 2.07 2.07 2.07

7.897 7.897 7.897 7.8977.878 7.878 7.878 7.878

7.260 7.260 7.260 7.260

6.962 6.962 6.962 6.9626.944 6.944 6.944 6.944

3.990 3.990 3.990 3.9903.986 3.986 3.986 3.9863.977 3.977 3.977 3.9773.973 3.973 3.973 3.9733.969 3.969 3.969 3.9693.965 3.965 3.965 3.9653.962 3.962 3.962 3.9623.950 3.950 3.950 3.9503.948 3.948 3.948 3.9483.943 3.943 3.943 3.9433.940 3.940 3.940 3.9403.937 3.937 3.937 3.9373.927 3.927 3.927 3.9273.923 3.923 3.923 3.9233.864 3.864 3.864 3.8643.828 3.828 3.828 3.8283.816 3.816 3.816 3.8163.805 3.805 3.805 3.8053.410 3.410 3.410 3.4103.398 3.398 3.398 3.3983.387 3.387 3.387 3.387

1.803 1.803 1.803 1.8031.791 1.791 1.791 1.7911.780 1.780 1.780 1.7801.670 1.670 1.670 1.6701.659 1.659 1.659 1.6591.647 1.647 1.647 1.647

MeO

O

N

O

3ae

CD

Cl 3

, 500

MH

z

O

O

~ S30 ~

Page 31: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

190.268 190.268 190.268 190.268

165.735 165.735 165.735 165.735164.829 164.829 164.829 164.829

131.960 131.960 131.960 131.960

126.122 126.122 126.122 126.122

114.304 114.304 114.304 114.304

106.626 106.626 106.626 106.626

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

64.486 64.486 64.486 64.486

55.586 55.586 55.586 55.586

43.988 43.988 43.988 43.988

39.228 39.228 39.228 39.228 35.289 35.289 35.289 35.289 34.640 34.640 34.640 34.640

MeO

O

N

O

3ae

CD

Cl 3

, 125

MH

z

O

O

~ S31 ~

Page 32: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

1.97 1.97 1.97 1.97

2.00 2.00 2.00 2.00

11.14 11.14 11.14 11.14

4.00 4.00 4.00 4.00

7.333 7.333 7.333 7.3337.320 7.320 7.320 7.3207.316 7.316 7.316 7.3167.260 7.260 7.260 7.2606.863 6.863 6.863 6.8636.859 6.859 6.859 6.8596.845 6.845 6.845 6.8456.842 6.842 6.842 6.842

3.918 3.918 3.918 3.9183.764 3.764 3.764 3.764

1.666 1.666 1.666 1.666

MeO

O

N

4ae

CD

Cl 3

, 12

5 M

HzO

O

~ S32 ~

Page 33: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

170.142 170.142 170.142 170.142

160.527 160.527 160.527 160.527

128.726 128.726 128.726 128.726127.858 127.858 127.858 127.858

113.503 113.503 113.503 113.503

106.798 106.798 106.798 106.798

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752

64.285 64.285 64.285 64.285

55.148 55.148 55.148 55.148

45.733 45.733 45.733 45.733

40.344 40.344 40.344 40.344 35.327 35.327 35.327 35.327 34.888 34.888 34.888 34.888

MeO

O

N

4ae

CD

Cl 3

, 12

5 M

HzO

O

~ S33 ~

Page 34: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

6.22 6.22 6.22 6.22

1.31 1.31 1.31 1.31

0.73 0.73 0.73 0.73

0.74 0.74 0.74 0.741.95 1.95 1.95 1.951.16 1.16 1.16 1.16

1.31 1.31 1.31 1.31

0.74 0.74 0.74 0.741.31 1.31 1.31 1.31

7.960 7.960 7.960 7.9607.954 7.954 7.954 7.9547.949 7.949 7.949 7.9497.940 7.940 7.940 7.9407.936 7.936 7.936 7.9367.930 7.930 7.930 7.9307.923 7.923 7.923 7.9237.920 7.920 7.920 7.9207.909 7.909 7.909 7.9097.906 7.906 7.906 7.9067.260 7.260 7.260 7.2607.251 7.251 7.251 7.2517.238 7.238 7.238 7.2387.233 7.233 7.233 7.2337.223 7.223 7.223 7.2237.221 7.221 7.221 7.2217.207 7.207 7.207 7.2077.195 7.195 7.195 7.1957.180 7.180 7.180 7.1807.168 7.168 7.168 7.1687.156 7.156 7.156 7.1567.151 7.151 7.151 7.1517.141 7.141 7.141 7.1417.136 7.136 7.136 7.1367.121 7.121 7.121 7.1217.107 7.107 7.107 7.1076.986 6.986 6.986 6.9866.981 6.981 6.981 6.9816.977 6.977 6.977 6.9776.967 6.967 6.967 6.9676.963 6.963 6.963 6.9636.958 6.958 6.958 6.9586.948 6.948 6.948 6.9486.945 6.945 6.945 6.9456.939 6.939 6.939 6.9396.935 6.935 6.935 6.9356.931 6.931 6.931 6.9316.926 6.926 6.926 6.9264.893 4.893 4.893 4.8934.532 4.532 4.532 4.5323.986 3.986 3.986 3.9863.974 3.974 3.974 3.9743.962 3.962 3.962 3.9623.877 3.877 3.877 3.8773.858 3.858 3.858 3.8583.622 3.622 3.622 3.6223.609 3.609 3.609 3.6093.598 3.598 3.598 3.5983.001 3.001 3.001 3.0012.988 2.988 2.988 2.9882.977 2.977 2.977 2.9772.859 2.859 2.859 2.8592.846 2.846 2.846 2.8462.835 2.835 2.835 2.835

MeO

O

N

O

3af

CD

Cl 3

, 500

MH

z

~ S34 ~

Page 35: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

190.144 190.144 190.144 190.144190.001 190.001 190.001 190.001

166.355 166.355 166.355 166.355166.040 166.040 166.040 166.040164.867 164.867 164.867 164.867164.829 164.829 164.829 164.829148.156 148.156 148.156 148.156146.201 146.201 146.201 146.201145.590 145.590 145.590 145.590134.135 134.135 134.135 134.135133.400 133.400 133.400 133.400132.122 132.122 132.122 132.122132.103 132.103 132.103 132.103131.836 131.836 131.836 131.836131.607 131.607 131.607 131.607128.879 128.879 128.879 128.879128.736 128.736 128.736 128.736127.067 127.067 127.067 127.067126.742 126.742 126.742 126.742126.695 126.695 126.695 126.695126.590 126.590 126.590 126.590126.494 126.494 126.494 126.494126.094 126.094 126.094 126.094126.008 126.008 126.008 126.008114.304 114.304 114.304 114.304114.285 114.285 114.285 114.285

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

55.577 55.577 55.577 55.577 55.558 55.558 55.558 55.558

47.279 47.279 47.279 47.279 43.444 43.444 43.444 43.444 43.292 43.292 43.292 43.292 39.190 39.190 39.190 39.190

29.175 29.175 29.175 29.175 28.192 28.192 28.192 28.192

MeO

O

N

O

3af

CD

Cl 3

, 125

MH

z

~ S35 ~

Page 36: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

1.94 1.94 1.94 1.94

1.01 1.01 1.01 1.012.00 2.00 2.00 2.00

3.01 3.01 3.01 3.01

2.08 2.08 2.08 2.08

5.32 5.32 5.32 5.32

3.02 3.02 3.02 3.02

8.433 8.433 8.433 8.4338.415 8.415 8.415 8.415

7.260 7.260 7.260 7.2607.117 7.117 7.117 7.1176.954 6.954 6.954 6.9546.936 6.936 6.936 6.936

3.891 3.891 3.891 3.891

3.401 3.401 3.401 3.4013.387 3.387 3.387 3.3873.374 3.374 3.374 3.3743.359 3.359 3.359 3.359

1.617 1.617 1.617 1.6171.602 1.602 1.602 1.6021.587 1.587 1.587 1.5871.572 1.572 1.572 1.5721.558 1.558 1.558 1.5581.442 1.442 1.442 1.4421.428 1.428 1.428 1.4281.413 1.413 1.413 1.4131.398 1.398 1.398 1.3981.383 1.383 1.383 1.3831.368 1.368 1.368 1.3680.969 0.969 0.969 0.9690.956 0.956 0.956 0.9560.941 0.941 0.941 0.941

MeO

OH N

O

3ag

CD

Cl 3

, 50

0 M

Hz

Me

~ S36 ~

Page 37: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

185.832 185.832 185.832 185.832

164.562 164.562 164.562 164.562162.254 162.254 162.254 162.254

133.829 133.829 133.829 133.829

126.342 126.342 126.342 126.342

113.713 113.713 113.713 113.713

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

55.462 55.462 55.462 55.462

39.009 39.009 39.009 39.009

31.254 31.254 31.254 31.254

19.989 19.989 19.989 19.989

13.637 13.637 13.637 13.637

MeO

OH N

O

3ag

CD

Cl 3

, 125

MH

z

Me

~ S37 ~

Page 38: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

2.04 2.04 2.04 2.04

0.95 0.95 0.95 0.95

3.12 3.12 3.12 3.12

2.06 2.06 2.06 2.06

3.02 3.02 3.02 3.022.20 2.20 2.20 2.20

3.12 3.12 3.12 3.12

7.732 7.732 7.732 7.7327.727 7.727 7.727 7.7277.718 7.718 7.718 7.7187.714 7.714 7.714 7.714

7.260 7.260 7.260 7.2606.924 6.924 6.924 6.9246.920 6.920 6.920 6.9206.911 6.911 6.911 6.9116.907 6.907 6.907 6.907

6.020 6.020 6.020 6.020

3.845 3.845 3.845 3.8453.461 3.461 3.461 3.4613.448 3.448 3.448 3.4483.436 3.436 3.436 3.4363.433 3.433 3.433 3.4333.421 3.421 3.421 3.421

1.621 1.621 1.621 1.6211.606 1.606 1.606 1.6061.591 1.591 1.591 1.5911.577 1.577 1.577 1.5771.561 1.561 1.561 1.5611.448 1.448 1.448 1.4481.433 1.433 1.433 1.4331.418 1.418 1.418 1.4181.402 1.402 1.402 1.4021.387 1.387 1.387 1.3871.372 1.372 1.372 1.3720.969 0.969 0.969 0.9690.954 0.954 0.954 0.9540.939 0.939 0.939 0.939

MeO

O

N H

4ag

CD

Cl 3

, 500

MH

z

Me

~ S38 ~

Page 39: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

166.985 166.985 166.985 166.985

161.996 161.996 161.996 161.996

128.555 128.555 128.555 128.555127.114 127.114 127.114 127.114

113.684 113.684 113.684 113.684

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752

55.386 55.386 55.386 55.386

39.724 39.724 39.724 39.724

31.807 31.807 31.807 31.807

20.161 20.161 20.161 20.161

13.809 13.809 13.809 13.809

MeO

O

N H

4ag

CD

Cl 3

, 125

MH

z

Me

~ S39 ~

Page 40: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

2.05 2.05 2.05 2.05

3.11 3.11 3.11 3.11

2.06 2.06 2.06 2.06

2.08 2.08 2.08 2.08

4.26 4.26 4.26 4.26

3.04 3.04 3.04 3.042.92 2.92 2.92 2.92

7.906 7.906 7.906 7.9067.889 7.889 7.889 7.889

7.260 7.260 7.260 7.260

6.967 6.967 6.967 6.9676.948 6.948 6.948 6.948

3.875 3.875 3.875 3.8753.459 3.459 3.459 3.4593.444 3.444 3.444 3.4443.428 3.428 3.428 3.4283.130 3.130 3.130 3.1303.115 3.115 3.115 3.1153.099 3.099 3.099 3.099

1.740 1.740 1.740 1.7401.725 1.725 1.725 1.7251.710 1.710 1.710 1.7101.695 1.695 1.695 1.6951.680 1.680 1.680 1.6801.666 1.666 1.666 1.6661.606 1.606 1.606 1.6061.591 1.591 1.591 1.5911.576 1.576 1.576 1.5761.560 1.560 1.560 1.5601.545 1.545 1.545 1.5451.530 1.530 1.530 1.5301.001 1.001 1.001 1.0010.986 0.986 0.986 0.9860.972 0.972 0.972 0.9720.792 0.792 0.792 0.7920.777 0.777 0.777 0.7770.762 0.762 0.762 0.762

MeO

ON

O

3ah

CD

Cl 3

, 500

MH

z

Me

Me

~ S40 ~

Page 41: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

2.05 2.05 2.05 2.05

3.11 3.11 3.11 3.11

2.07 2.07 2.07 2.07

2.09 2.09 2.09 2.09

2.20 2.20 2.20 2.202.06 2.06 2.06 2.06

3.04 3.04 3.04 3.042.92 2.92 2.92 2.92

7.906 7.906 7.906 7.9067.889 7.889 7.889 7.889

7.260 7.260 7.260 7.260

6.967 6.967 6.967 6.9676.948 6.948 6.948 6.948

3.875 3.875 3.875 3.8753.459 3.459 3.459 3.4593.444 3.444 3.444 3.4443.428 3.428 3.428 3.4283.130 3.130 3.130 3.1303.115 3.115 3.115 3.1153.099 3.099 3.099 3.099

1.740 1.740 1.740 1.7401.725 1.725 1.725 1.7251.710 1.710 1.710 1.7101.695 1.695 1.695 1.6951.680 1.680 1.680 1.6801.666 1.666 1.666 1.6661.606 1.606 1.606 1.6061.591 1.591 1.591 1.5911.576 1.576 1.576 1.5761.560 1.560 1.560 1.5601.545 1.545 1.545 1.5451.530 1.530 1.530 1.5301.244 1.244 1.244 1.2441.001 1.001 1.001 1.0010.986 0.986 0.986 0.9860.972 0.972 0.972 0.9720.792 0.792 0.792 0.7920.777 0.777 0.777 0.7770.762 0.762 0.762 0.762

MeO

ON

O

3ah

CD

Cl 3

, 500

MH

z

Me

Me

~ S41 ~

Page 42: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

190.296 190.296 190.296 190.296

167.481 167.481 167.481 167.481164.610 164.610 164.610 164.610

132.027 132.027 132.027 132.027

126.418 126.418 126.418 126.418

114.190 114.190 114.190 114.190

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752

55.577 55.577 55.577 55.577

49.301 49.301 49.301 49.301 45.743 45.743 45.743 45.743

21.773 21.773 21.773 21.773 20.590 20.590 20.590 20.590

11.395 11.395 11.395 11.395 11.004 11.004 11.004 11.004

MeO

ON

O

3ah

CD

Cl 3

, 125

MH

z

Me

Me

~ S42 ~

Page 43: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

2.02 2.02 2.02 2.02

3.10 3.10 3.10 3.10

4.38 4.38 4.38 4.38

4.33 4.33 4.33 4.33

6.36 6.36 6.36 6.36

7.328 7.328 7.328 7.3287.323 7.323 7.323 7.3237.318 7.318 7.318 7.3187.309 7.309 7.309 7.3097.305 7.305 7.305 7.3057.299 7.299 7.299 7.2997.260 7.260 7.260 7.2606.898 6.898 6.898 6.8986.894 6.894 6.894 6.8946.889 6.889 6.889 6.8896.880 6.880 6.880 6.8806.875 6.875 6.875 6.8756.869 6.869 6.869 6.869

3.818 3.818 3.818 3.818

3.412 3.412 3.412 3.412

3.206 3.206 3.206 3.206

1.642 1.642 1.642 1.6421.547 1.547 1.547 1.547

0.941 0.941 0.941 0.9410.756 0.756 0.756 0.756

MeO

O

N

4ah

CD

Cl 3

, 500

MH

z

Me

Me

~ S43 ~

Page 44: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

171.658 171.658 171.658 171.658

160.107 160.107 160.107 160.107

129.604 129.604 129.604 129.604128.297 128.297 128.297 128.297

113.560 113.560 113.560 113.560

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

55.253 55.253 55.253 55.253

50.855 50.855 50.855 50.855

46.458 46.458 46.458 46.458

21.945 21.945 21.945 21.945 20.638 20.638 20.638 20.638

11.224 11.224 11.224 11.224

MeO

O

N

4ah

CD

Cl 3

, 125

MH

z

Me

Me

~ S44 ~

Page 45: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

5.52 5.52 5.52 5.52

2.07 2.07 2.07 2.07

2.08 2.08 2.08 2.08

3.20 3.20 3.20 3.20

3.16 3.16 3.16 3.16

7.973 7.973 7.973 7.9737.969 7.969 7.969 7.9697.955 7.955 7.955 7.9557.949 7.949 7.949 7.9497.940 7.940 7.940 7.9407.937 7.937 7.937 7.9377.923 7.923 7.923 7.9237.399 7.399 7.399 7.3997.384 7.384 7.384 7.3847.370 7.370 7.370 7.3707.363 7.363 7.363 7.3637.350 7.350 7.350 7.3507.338 7.338 7.338 7.3387.324 7.324 7.324 7.3247.321 7.321 7.321 7.3217.309 7.309 7.309 7.3097.296 7.296 7.296 7.2967.282 7.282 7.282 7.2827.263 7.263 7.263 7.2637.260 7.260 7.260 7.2607.246 7.246 7.246 7.2466.985 6.985 6.985 6.9856.983 6.983 6.983 6.9836.967 6.967 6.967 6.9676.965 6.965 6.965 6.965

4.722 4.722 4.722 4.722

4.392 4.392 4.392 4.392

3.884 3.884 3.884 3.8843.880 3.880 3.880 3.880

2.971 2.971 2.971 2.9712.836 2.836 2.836 2.836

MeO

O

N

O

Me

3ai

CD

Cl 3

, 500

MH

z

~ S45 ~

Page 46: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

190.182 190.182 190.182 190.182

167.624 167.624 167.624 167.624167.433 167.433 167.433 167.433164.829 164.829 164.829 164.829164.810 164.810 164.810 164.810

135.861 135.861 135.861 135.861135.031 135.031 135.031 135.031132.208 132.208 132.208 132.208132.074 132.074 132.074 132.074128.822 128.822 128.822 128.822128.755 128.755 128.755 128.755128.278 128.278 128.278 128.278128.106 128.106 128.106 128.106127.792 127.792 127.792 127.792126.275 126.275 126.275 126.275126.103 126.103 126.103 126.103114.323 114.323 114.323 114.323114.266 114.266 114.266 114.266

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752

55.606 55.606 55.606 55.606 53.526 53.526 53.526 53.526 49.730 49.730 49.730 49.730

34.469 34.469 34.469 34.469 31.273 31.273 31.273 31.273

MeO

O

N

O

Me

3ai

CD

Cl 3

, 125

MH

z

~ S46 ~

Page 47: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

2.07 2.07 2.07 2.07

1.11 1.11 1.11 1.113.02 3.02 3.02 3.020.96 0.96 0.96 0.961.02 1.02 1.02 1.02

0.97 0.97 0.97 0.97

1.47 1.47 1.47 1.471.59 1.59 1.59 1.59

9.50 9.50 9.50 9.50

6.18 6.18 6.18 6.18

7.927 7.927 7.927 7.9277.921 7.921 7.921 7.9217.915 7.915 7.915 7.9157.910 7.910 7.910 7.9107.907 7.907 7.907 7.9077.904 7.904 7.904 7.9047.897 7.897 7.897 7.8977.891 7.891 7.891 7.8917.260 7.260 7.260 7.2606.961 6.961 6.961 6.9616.957 6.957 6.957 6.9576.951 6.951 6.951 6.9516.947 6.947 6.947 6.9476.943 6.943 6.943 6.9436.937 6.937 6.937 6.9376.934 6.934 6.934 6.934

3.910 3.910 3.910 3.9103.900 3.900 3.900 3.9003.888 3.888 3.888 3.8883.872 3.872 3.872 3.8723.867 3.867 3.867 3.8673.713 3.713 3.713 3.7133.702 3.702 3.702 3.7023.690 3.690 3.690 3.6903.643 3.643 3.643 3.6433.633 3.633 3.633 3.6333.623 3.623 3.623 3.6233.351 3.351 3.351 3.3513.340 3.340 3.340 3.3403.328 3.328 3.328 3.3283.147 3.147 3.147 3.1473.018 3.018 3.018 3.018

0.896 0.896 0.896 0.8960.831 0.831 0.831 0.831

0.091 0.091 0.091 0.091-0.025 -0.025 -0.025 -0.025

MeO

ON

O

Me

3aj

CD

Cl 3

, 500

MH

z

OT

BS

~ S47 ~

Page 48: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

190.458 190.458 190.458 190.458

167.748 167.748 167.748 167.748167.509 167.509 167.509 167.509164.705 164.705 164.705 164.705

132.246 132.246 132.246 132.246132.065 132.065 132.065 132.065126.294 126.294 126.294 126.294126.113 126.113 126.113 126.113

114.247 114.247 114.247 114.247114.152 114.152 114.152 114.152

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752

61.586 61.586 61.586 61.586 61.090 61.090 61.090 61.090

55.577 55.577 55.577 55.577 51.800 51.800 51.800 51.800 49.291 49.291 49.291 49.291

36.987 36.987 36.987 36.987 33.353 33.353 33.353 33.353

25.817 25.817 25.817 25.817 25.779 25.779 25.779 25.779

18.149 18.149 18.149 18.149

-5.497 -5.497 -5.497 -5.497 -5.602 -5.602 -5.602 -5.602

MeO

ON

O

Me

3aj

CD

Cl 3

, 125

MH

z

OT

BS

~ S48 ~

Page 49: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.0

10.0

10.0

10.0

9.59.59.59.5

9.09.09.09.0

8.58.58.58.5

8.08.08.08.0

7.57.57.57.5

7.07.07.07.0

6.56.56.56.5

6.06.06.06.0

5.55.55.55.5

5.05.05.05.0

4.54.54.54.5

4.04.04.04.0

3.53.53.53.5

3.03.03.03.0

2.52.52.52.5

2.02.02.02.0

1.51.51.51.5

1.01.01.01.0

0.50.50.50.5

0.00.00.00.0

2.00 2.00 2.00 2.000.94 0.94 0.94 0.941.98 1.98 1.98 1.98

1.98 1.98 1.98 1.98

1.01 1.01 1.01 1.011.99 1.99 1.99 1.99

2.99 2.99 2.99 2.99

7.857 7.857 7.857 7.8577.839 7.839 7.839 7.8397.704 7.704 7.704 7.7047.637 7.637 7.637 7.6377.622 7.622 7.622 7.6227.388 7.388 7.388 7.3887.373 7.373 7.373 7.3737.356 7.356 7.356 7.3567.260 7.260 7.260 7.2607.158 7.158 7.158 7.1587.143 7.143 7.143 7.1437.128 7.128 7.128 7.1286.995 6.995 6.995 6.9956.977 6.977 6.977 6.977

3.882 3.882 3.882 3.882

MeO

O 4ak

CD

Cl 3

, 500

MH

z

N H

~ S49 ~

Page 50: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

165.201 165.201 165.201 165.201162.444 162.444 162.444 162.444

138.093 138.093 138.093 138.093

129.041 129.041 129.041 129.041128.888 128.888 128.888 128.888127.114 127.114 127.114 127.114124.301 124.301 124.301 124.301120.123 120.123 120.123 120.123

113.942 113.942 113.942 113.942

77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

55.453 55.453 55.453 55.453

MeO

O 4ak

CD

Cl 3

, 125

MH

z

N H

~ S50 ~

Page 51: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

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㻞㻚㻝㻠 㻞㻚㻝㻠 㻞㻚㻝㻠 㻞㻚㻝㻠

㻣㻚㻠㻤㻠 㻣㻚㻠㻤㻠 㻣㻚㻠㻤㻠 㻣㻚㻠㻤㻠㻣㻚㻠㻤㻞 㻣㻚㻠㻤㻞 㻣㻚㻠㻤㻞 㻣㻚㻠㻤㻞㻣㻚㻠㻢㻢 㻣㻚㻠㻢㻢 㻣㻚㻠㻢㻢 㻣㻚㻠㻢㻢㻣㻚㻠㻢㻜 㻣㻚㻠㻢㻜 㻣㻚㻠㻢㻜 㻣㻚㻠㻢㻜㻣㻚㻠㻝㻞 㻣㻚㻠㻝㻞 㻣㻚㻠㻝㻞 㻣㻚㻠㻝㻞㻣㻚㻟㻥㻢 㻣㻚㻟㻥㻢 㻣㻚㻟㻥㻢 㻣㻚㻟㻥㻢㻣㻚㻟㻤㻜 㻣㻚㻟㻤㻜 㻣㻚㻟㻤㻜 㻣㻚㻟㻤㻜㻣㻚㻞㻢㻜 㻣㻚㻞㻢㻜 㻣㻚㻞㻢㻜 㻣㻚㻞㻢㻜㻣㻚㻝㻤㻟 㻣㻚㻝㻤㻟 㻣㻚㻝㻤㻟 㻣㻚㻝㻤㻟㻣㻚㻝㻤㻝 㻣㻚㻝㻤㻝 㻣㻚㻝㻤㻝 㻣㻚㻝㻤㻝㻣㻚㻝㻣㻢 㻣㻚㻝㻣㻢 㻣㻚㻝㻣㻢 㻣㻚㻝㻣㻢㻣㻚㻝㻢㻣 㻣㻚㻝㻢㻣 㻣㻚㻝㻢㻣 㻣㻚㻝㻢㻣㻣㻚㻝㻢㻡 㻣㻚㻝㻢㻡 㻣㻚㻝㻢㻡 㻣㻚㻝㻢㻡㻣㻚㻝㻢㻞 㻣㻚㻝㻢㻞 㻣㻚㻝㻢㻞 㻣㻚㻝㻢㻞㻣㻚㻝㻡㻥 㻣㻚㻝㻡㻥 㻣㻚㻝㻡㻥 㻣㻚㻝㻡㻥

㻟㻚㻤㻟㻠 㻟㻚㻤㻟㻠 㻟㻚㻤㻟㻠 㻟㻚㻤㻟㻠㻟㻚㻣㻤㻝 㻟㻚㻣㻤㻝 㻟㻚㻣㻤㻝 㻟㻚㻣㻤㻝㻟㻚㻣㻣㻡 㻟㻚㻣㻣㻡 㻟㻚㻣㻣㻡 㻟㻚㻣㻣㻡㻟㻚㻣㻢㻡 㻟㻚㻣㻢㻡 㻟㻚㻣㻢㻡 㻟㻚㻣㻢㻡㻟㻚㻣㻢㻜 㻟㻚㻣㻢㻜 㻟㻚㻣㻢㻜 㻟㻚㻣㻢㻜㻟㻚㻣㻡㻣 㻟㻚㻣㻡㻣 㻟㻚㻣㻡㻣 㻟㻚㻣㻡㻣㻟㻚㻣㻡㻞 㻟㻚㻣㻡㻞 㻟㻚㻣㻡㻞 㻟㻚㻣㻡㻞㻟㻚㻣㻠㻤 㻟㻚㻣㻠㻤 㻟㻚㻣㻠㻤 㻟㻚㻣㻠㻤㻟㻚㻣㻠㻞 㻟㻚㻣㻠㻞 㻟㻚㻣㻠㻞 㻟㻚㻣㻠㻞㻟㻚㻣㻟㻢 㻟㻚㻣㻟㻢 㻟㻚㻣㻟㻢 㻟㻚㻣㻟㻢㻟㻚㻢㻟㻟 㻟㻚㻢㻟㻟 㻟㻚㻢㻟㻟 㻟㻚㻢㻟㻟㻟㻚㻢㻞㻥 㻟㻚㻢㻞㻥 㻟㻚㻢㻞㻥 㻟㻚㻢㻞㻥㻟㻚㻢㻞㻟 㻟㻚㻢㻞㻟 㻟㻚㻢㻞㻟 㻟㻚㻢㻞㻟㻟㻚㻢㻝㻣 㻟㻚㻢㻝㻣 㻟㻚㻢㻝㻣 㻟㻚㻢㻝㻣㻟㻚㻢㻝㻠 㻟㻚㻢㻝㻠 㻟㻚㻢㻝㻠 㻟㻚㻢㻝㻠㻟㻚㻟㻡㻜 㻟㻚㻟㻡㻜 㻟㻚㻟㻡㻜 㻟㻚㻟㻡㻜㻟㻚㻟㻠㻣 㻟㻚㻟㻠㻣 㻟㻚㻟㻠㻣 㻟㻚㻟㻠㻣㻟㻚㻟㻠㻝 㻟㻚㻟㻠㻝 㻟㻚㻟㻠㻝 㻟㻚㻟㻠㻝㻟㻚㻟㻟㻡 㻟㻚㻟㻟㻡 㻟㻚㻟㻟㻡 㻟㻚㻟㻟㻡㻟㻚㻟㻟㻝 㻟㻚㻟㻟㻝 㻟㻚㻟㻟㻝 㻟㻚㻟㻟㻝

ON

O

O

3ba

CD

Cl 3,

500

MH

z

MeO

~ S51 ~

Page 52: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

190.993 190.993 190.993 190.993

165.296 165.296 165.296 165.296

160.022 160.022 160.022 160.022

134.192 134.192 134.192 134.192

130.052 130.052 130.052 130.052

122.698 122.698 122.698 122.698121.706 121.706 121.706 121.706

112.645 112.645 112.645 112.645

77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.584 66.584 66.584 66.584 66.536 66.536 66.536 66.536

55.434 55.434 55.434 55.434

46.134 46.134 46.134 46.134

41.479 41.479 41.479 41.479

ON

O

O

3ba

CD

Cl 3

, 125

MH

z

MeO

~ S52 ~

Page 53: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

0.97 0.97 0.97 0.97

3.00 3.00 3.00 3.00

11.36 11.36 11.36 11.36

7.323 7.323 7.323 7.3237.306 7.306 7.306 7.3067.291 7.291 7.291 7.2917.260 7.260 7.260 7.2606.955 6.955 6.955 6.9556.951 6.951 6.951 6.9516.934 6.934 6.934 6.934

3.814 3.814 3.814 3.8143.808 3.808 3.808 3.8083.763 3.763 3.763 3.7633.614 3.614 3.614 3.6143.437 3.437 3.437 3.437

O

N

O

4ba

CD

Cl 3

, 500

MH

z

MeO

~ S53 ~

Page 54: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

170.161 170.161 170.161 170.161

159.688 159.688 159.688 159.688

136.595 136.595 136.595 136.595

129.661 129.661 129.661 129.661

119.054 119.054 119.054 119.054115.630 115.630 115.630 115.630112.483 112.483 112.483 112.483

77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.899 66.899 66.899 66.899

55.358 55.358 55.358 55.358

48.204 48.204 48.204 48.204

42.548 42.548 42.548 42.548

O

N

O

4ba

CD

Cl 3

, 125

MH

z

MeO

~ S54 ~

Page 55: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.0

10.0

10.0

10.0

9.59.59.59.5

9.09.09.09.0

8.58.58.58.5

8.08.08.08.0

7.57.57.57.5

7.07.07.07.0

6.56.56.56.5

6.06.06.06.0

5.55.55.55.5

5.05.05.05.0

4.54.54.54.5

4.04.04.04.0

3.53.53.53.5

3.03.03.03.0

2.52.52.52.5

2.02.02.02.0

1.51.51.51.5

1.01.01.01.0

0.50.50.50.5

0.00.00.00.0

-0.5

-0.5

-0.5

-0.5

1.00 1.00 1.00 1.00

1.02 1.02 1.02 1.02

0.99 0.99 0.99 0.991.03 1.03 1.03 1.03

3.23 3.23 3.23 3.232.25 2.25 2.25 2.25

4.34 4.34 4.34 4.34

2.10 2.10 2.10 2.10

7.937 7.937 7.937 7.9377.933 7.933 7.933 7.9337.921 7.921 7.921 7.9217.917 7.917 7.917 7.9177.600 7.600 7.600 7.6007.597 7.597 7.597 7.5977.583 7.583 7.583 7.5837.569 7.569 7.569 7.5697.566 7.566 7.566 7.5667.260 7.260 7.260 7.2607.107 7.107 7.107 7.1077.091 7.091 7.091 7.0917.074 7.074 7.074 7.0747.003 7.003 7.003 7.0036.987 6.987 6.987 6.987

3.909 3.909 3.909 3.9093.805 3.805 3.805 3.8053.796 3.796 3.796 3.7963.785 3.785 3.785 3.7853.728 3.728 3.728 3.7283.717 3.717 3.717 3.7173.710 3.710 3.710 3.7103.701 3.701 3.701 3.7013.690 3.690 3.690 3.6903.417 3.417 3.417 3.4173.406 3.406 3.406 3.4063.397 3.397 3.397 3.397

O

N

O

O

3ca

CD

Cl 3

, 500

MH

z

OM

e

~ S55 ~

Page 56: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

190.234 190.234 190.234 190.234

167.371 167.371 167.371 167.371

160.136 160.136 160.136 160.136

136.223 136.223 136.223 136.223

131.116 131.116 131.116 131.116

123.528 123.528 123.528 123.528121.453 121.453 121.453 121.453

112.206 112.206 112.206 112.206

77.253 77.253 77.253 77.253 77.000 77.000 77.000 77.000 76.747 76.747 76.747 76.747

66.546 66.546 66.546 66.546 66.336 66.336 66.336 66.336

56.216 56.216 56.216 56.216

45.881 45.881 45.881 45.881

41.379 41.379 41.379 41.379

O

N

O

O

3ca

CD

Cl 3

, 125

MH

z

OM

e

~ S56 ~

Page 57: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00

1.00 1.00 1.00 1.00 0.97 0.97 0.97 0.97

1.00 1.00 1.00 1.000.96 0.96 0.96 0.96

7.31 7.31 7.31 7.312.04 2.04 2.04 2.04

2.00 2.00 2.00 2.00

7.368 7.368 7.368 7.3687.364 7.364 7.364 7.3647.353 7.353 7.353 7.3537.349 7.349 7.349 7.3497.337 7.337 7.337 7.3377.333 7.333 7.333 7.3337.260 7.260 7.260 7.2607.252 7.252 7.252 7.2527.249 7.249 7.249 7.2497.236 7.236 7.236 7.2367.234 7.234 7.234 7.2347.005 7.005 7.005 7.0056.990 6.990 6.990 6.9906.975 6.975 6.975 6.9756.915 6.915 6.915 6.9156.898 6.898 6.898 6.898

3.832 3.832 3.832 3.8323.785 3.785 3.785 3.7853.765 3.765 3.765 3.7653.754 3.754 3.754 3.7543.736 3.736 3.736 3.7363.720 3.720 3.720 3.7203.628 3.628 3.628 3.6283.616 3.616 3.616 3.6163.609 3.609 3.609 3.6093.571 3.571 3.571 3.5713.564 3.564 3.564 3.5643.285 3.285 3.285 3.2853.277 3.277 3.277 3.2773.240 3.240 3.240 3.2403.230 3.230 3.230 3.2303.222 3.222 3.222 3.222

O

N

O

4ca

CD

Cl 3

, 500

MH

z

OM

e

~ S57 ~

Page 58: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

167.833 167.833 167.833 167.833

155.176 155.176 155.176 155.176

130.567 130.567 130.567 130.567128.030 128.030 128.030 128.030125.159 125.159 125.159 125.159

120.962 120.962 120.962 120.962

110.823 110.823 110.823 110.823

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.908 66.908 66.908 66.908 66.784 66.784 66.784 66.784

55.462 55.462 55.462 55.462

47.221 47.221 47.221 47.221

42.052 42.052 42.052 42.052

O

N

O

4ca

CD

Cl 3

, 125

MH

z

OM

e

~ S58 ~

Page 59: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

0.98 0.98 0.98 0.98

4.19 4.19 4.19 4.192.10 2.10 2.10 2.10

2.02 2.02 2.02 2.02

6.36 6.36 6.36 6.36

7.544 7.544 7.544 7.544

7.275 7.275 7.275 7.2757.260 7.260 7.260 7.260

3.801 3.801 3.801 3.8013.796 3.796 3.796 3.7963.782 3.782 3.782 3.7823.780 3.780 3.780 3.7803.772 3.772 3.772 3.7723.766 3.766 3.766 3.7663.759 3.759 3.759 3.7593.648 3.648 3.648 3.6483.639 3.639 3.639 3.6393.628 3.628 3.628 3.6283.362 3.362 3.362 3.3623.352 3.352 3.352 3.3523.343 3.343 3.343 3.343

2.365 2.365 2.365 2.365

O

N

O

O

3da

CD

Cl 3

, 500

MH

z

Me

Me

~ S59 ~

Page 60: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

191.574 191.574 191.574 191.574

165.659 165.659 165.659 165.659

138.866 138.866 138.866 138.866136.739 136.739 136.739 136.739132.990 132.990 132.990 132.990

127.267 127.267 127.267 127.267

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.670 66.670 66.670 66.670 66.613 66.613 66.613 66.613

46.201 46.201 46.201 46.201

41.517 41.517 41.517 41.517

21.096 21.096 21.096 21.096

O

N

O

O

3da

CD

Cl 3

, 125

MH

z

Me

Me

~ S60 ~

Page 61: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

3.00 3.00 3.00 3.00

8.47 8.47 8.47 8.47

6.37 6.37 6.37 6.37

7.260 7.260 7.260 7.2607.041 7.041 7.041 7.0416.990 6.990 6.990 6.990

3.766 3.766 3.766 3.7663.616 3.616 3.616 3.6163.447 3.447 3.447 3.447

2.327 2.327 2.327 2.327

O

N

O

4da

CD

Cl 3

, 500

MH

z

Me

Me

~ S61 ~

Page 62: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

170.781 170.781 170.781 170.781

138.255 138.255 138.255 138.255135.270 135.270 135.270 135.270

131.349 131.349 131.349 131.349

124.577 124.577 124.577 124.577

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.918 66.918 66.918 66.918

48.194 48.194 48.194 48.194

42.471 42.471 42.471 42.471

21.239 21.239 21.239 21.239

O

N

O

4da

CD

Cl 3

, 125

MH

z

Me

Me

~ S62 ~

Page 63: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

9.22 9.22 9.22 9.224.12 4.12 4.12 4.12

2.04 2.04 2.04 2.04

1.92 1.92 1.92 1.92

7.260 7.260 7.260 7.2607.174 7.174 7.174 7.174

3.908 3.908 3.908 3.9083.877 3.877 3.877 3.8773.753 3.753 3.753 3.7533.641 3.641 3.641 3.6413.636 3.636 3.636 3.6363.631 3.631 3.631 3.6313.622 3.622 3.622 3.6223.359 3.359 3.359 3.3593.349 3.349 3.349 3.3493.340 3.340 3.340 3.340

O

N

O

O

3ea

CD

Cl 3

, 125

MH

z

MeO

OM

e

MeO

~ S63 ~

Page 64: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

189.915 189.915 189.915 189.915

165.229 165.229 165.229 165.229

153.316 153.316 153.316 153.316

144.140 144.140 144.140 144.140

127.896 127.896 127.896 127.896

106.788 106.788 106.788 106.788

77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.670 66.670 66.670 66.670 66.613 66.613 66.613 66.613

60.928 60.928 60.928 60.928

56.264 56.264 56.264 56.264

46.229 46.229 46.229 46.229

41.584 41.584 41.584 41.584

O

N

O

O

3ea

CD

Cl 3

, 125

MH

z

MeO

OM

e

MeO

~ S64 ~

Page 65: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

17.13 17.13 17.13 17.13

7.260 7.260 7.260 7.260

6.612 6.612 6.612 6.612

3.859 3.859 3.859 3.8593.843 3.843 3.843 3.8433.712 3.712 3.712 3.712

O

N

O

4ea

CD

Cl 3

, 500

MH

z

MeO

OM

e

MeO

~ S65 ~

Page 66: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

170.123 170.123 170.123 170.123

153.316 153.316 153.316 153.316

139.238 139.238 139.238 139.238

130.596 130.596 130.596 130.596

104.280 104.280 104.280 104.280

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.851 66.851 66.851 66.851

60.852 60.852 60.852 60.852

56.216 56.216 56.216 56.216

48.290 48.290 48.290 48.290

42.662 42.662 42.662 42.662

O

N

O

4ea

CD

Cl 3

, 125

MH

z

MeO

OM

e

MeO

~ S66 ~

Page 67: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

1.04 1.04 1.04 1.042.07 2.07 2.07 2.07

4.14 4.14 4.14 4.142.11 2.11 2.11 2.11

2.08 2.08 2.08 2.08

7.971 7.971 7.971 7.9717.957 7.957 7.957 7.9577.955 7.955 7.955 7.9557.678 7.678 7.678 7.6787.676 7.676 7.676 7.6767.663 7.663 7.663 7.6637.648 7.648 7.648 7.6487.646 7.646 7.646 7.6467.544 7.544 7.544 7.5447.541 7.541 7.541 7.5417.528 7.528 7.528 7.5287.517 7.517 7.517 7.5177.513 7.513 7.513 7.5137.260 7.260 7.260 7.260

3.820 3.820 3.820 3.8203.814 3.814 3.814 3.8143.800 3.800 3.800 3.8003.791 3.791 3.791 3.7913.779 3.779 3.779 3.7793.670 3.670 3.670 3.6703.661 3.661 3.661 3.6613.650 3.650 3.650 3.6503.397 3.397 3.397 3.3973.388 3.388 3.388 3.3883.378 3.378 3.378 3.378

ON

O

O

3fa

CD

Cl 3

, 500

MH

z

~ S67 ~

Page 68: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

190.954 190.954 190.954 190.954

165.172 165.172 165.172 165.172

134.726 134.726 134.726 134.726132.742 132.742 132.742 132.742129.365 129.365 129.365 129.365128.860 128.860 128.860 128.860

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.422 66.422 66.422 66.422 66.346 66.346 66.346 66.346

45.962 45.962 45.962 45.962

41.308 41.308 41.308 41.308

ON

O

O

3fa

CD

Cl 3

, 125

MH

z

~ S68 ~

Page 69: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

5.00 5.00 5.00 5.00

8.43 8.43 8.43 8.43

7.417 7.417 7.417 7.4177.407 7.407 7.407 7.4077.260 7.260 7.260 7.260

3.773 3.773 3.773 3.7733.625 3.625 3.625 3.6253.444 3.444 3.444 3.444

O

N

O

4fa

CD

Cl 3

, 500

MH

z

~ S69 ~

Page 70: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

170.418 170.418 170.418 170.418

135.279 135.279 135.279 135.279

129.861 129.861 129.861 129.861128.555 128.555 128.555 128.555127.067 127.067 127.067 127.067

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752

66.889 66.889 66.889 66.889

48.194 48.194 48.194 48.194

42.471 42.471 42.471 42.471

O

N

O

4fa

CD

Cl 3

, 125

MH

z

~ S70 ~

Page 71: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

2.03 2.03 2.03 2.03

4.22 4.22 4.22 4.222.13 2.13 2.13 2.13

2.05 2.05 2.05 2.05

7.906 7.906 7.906 7.9067.901 7.901 7.901 7.9017.898 7.898 7.898 7.8987.889 7.889 7.889 7.8897.884 7.884 7.884 7.8847.880 7.880 7.880 7.8807.496 7.496 7.496 7.4967.491 7.491 7.491 7.4917.487 7.487 7.487 7.4877.478 7.478 7.478 7.4787.474 7.474 7.474 7.4747.260 7.260 7.260 7.260

3.793 3.793 3.793 3.7933.788 3.788 3.788 3.7883.777 3.777 3.777 3.7773.773 3.773 3.773 3.7733.767 3.767 3.767 3.7673.762 3.762 3.762 3.7623.752 3.752 3.752 3.7523.748 3.748 3.748 3.7483.654 3.654 3.654 3.6543.649 3.649 3.649 3.6493.643 3.643 3.643 3.6433.638 3.638 3.638 3.6383.634 3.634 3.634 3.6343.375 3.375 3.375 3.3753.365 3.365 3.365 3.3653.356 3.356 3.356 3.356

O

N

O

O

3ga

CD

Cl 3

, 500

MH

z

Cl

~ S71 ~

Page 72: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

189.648 189.648 189.648 189.648

164.829 164.829 164.829 164.829

141.546 141.546 141.546 141.546

131.397 131.397 131.397 131.397130.977 130.977 130.977 130.977129.442 129.442 129.442 129.442

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752

66.680 66.680 66.680 66.680 66.575 66.575 66.575 66.575

46.220 46.220 46.220 46.220

41.641 41.641 41.641 41.641

O

N

O

O

3ga

CD

Cl 3

, 125

MH

z

Cl

~ S72 ~

Page 73: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

4.00 4.00 4.00 4.00

8.19 8.19 8.19 8.19

7.407 7.407 7.407 7.4077.403 7.403 7.403 7.4037.394 7.394 7.394 7.3947.389 7.389 7.389 7.3897.386 7.386 7.386 7.3867.364 7.364 7.364 7.3647.360 7.360 7.360 7.3607.352 7.352 7.352 7.3527.347 7.347 7.347 7.3477.260 7.260 7.260 7.260

3.740 3.740 3.740 3.740

3.453 3.453 3.453 3.453

O

N

O

4ga

CD

Cl 3

, 500

MH

z

Cl

~ S73 ~

Page 74: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

169.321 169.321 169.321 169.321

135.995 135.995 135.995 135.995133.591 133.591 133.591 133.591128.841 128.841 128.841 128.841128.640 128.640 128.640 128.640

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752

66.804 66.804 66.804 66.804

48.175 48.175 48.175 48.175

42.605 42.605 42.605 42.605

O

N

O

4ga

CD

Cl 3

, 125

MH

z

Cl

~ S74 ~

Page 75: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00

2.00 2.00 2.00 2.001.99 1.99 1.99 1.99

3.03 3.03 3.03 3.034.03 4.03 4.03 4.03

2.06 2.06 2.06 2.06

1.88 1.88 1.88 1.88

8.166 8.166 8.166 8.1668.149 8.149 8.149 8.1498.025 8.025 8.025 8.0258.008 8.008 8.008 8.008

7.260 7.260 7.260 7.260

3.949 3.949 3.949 3.9493.791 3.791 3.791 3.7913.666 3.666 3.666 3.6663.656 3.656 3.656 3.6563.647 3.647 3.647 3.6473.393 3.393 3.393 3.3933.382 3.382 3.382 3.3823.373 3.373 3.373 3.373

O

N

O

O

3ha

CD

Cl 3

, 500

MH

z

MeO

2C

~ S75 ~

Page 76: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

190.210 190.210 190.210 190.210

165.792 165.792 165.792 165.792164.762 164.762 164.762 164.762

136.080 136.080 136.080 136.080135.327 135.327 135.327 135.327130.119 130.119 130.119 130.119129.547 129.547 129.547 129.547

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752

66.680 66.680 66.680 66.680 66.594 66.594 66.594 66.594

52.611 52.611 52.611 52.611

46.229 46.229 46.229 46.229

41.699 41.699 41.699 41.699

O

N

O

O

3ha

CD

Cl 3

, 125

MH

z

MeO

2C

~ S76 ~

Page 77: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

2.00 2.00 2.00 2.00

1.97 1.97 1.97 1.97

11.09 11.09 11.09 11.09

8.087 8.087 8.087 8.0878.071 8.071 8.071 8.071

7.470 7.470 7.470 7.4707.454 7.454 7.454 7.4547.260 7.260 7.260 7.260

3.925 3.925 3.925 3.9253.776 3.776 3.776 3.7763.608 3.608 3.608 3.608

3.385 3.385 3.385 3.385

O

N

O

4ha

CD

Cl 3

, 500

MH

z

MeO

2C

~ S77 ~

Page 78: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

169.331 169.331 169.331 169.331166.212 166.212 166.212 166.212

139.524 139.524 139.524 139.524

131.292 131.292 131.292 131.292129.852 129.852 129.852 129.852127.019 127.019 127.019 127.019

77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.775 66.775 66.775 66.775

52.334 52.334 52.334 52.334

48.023 48.023 48.023 48.023

42.471 42.471 42.471 42.471

O

N

O

4ha

CD

Cl 3

, 125

MH

z

MeO

2C

~ S78 ~

Page 79: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

0.92 0.92 0.92 0.92

1.00 1.00 1.00 1.00

1.02 1.02 1.02 1.02

4.16 4.16 4.16 4.162.09 2.09 2.09 2.09

2.03 2.03 2.03 2.03

6.43 6.43 6.43 6.43

8.525 8.525 8.525 8.5258.521 8.521 8.521 8.5218.216 8.216 8.216 8.2168.212 8.212 8.212 8.2128.199 8.199 8.199 8.1998.195 8.195 8.195 8.195

7.260 7.260 7.260 7.2607.109 7.109 7.109 7.1097.092 7.092 7.092 7.092

3.817 3.817 3.817 3.8173.814 3.814 3.814 3.8143.811 3.811 3.811 3.8113.806 3.806 3.806 3.8063.803 3.803 3.803 3.8033.797 3.797 3.797 3.7973.788 3.788 3.788 3.7883.782 3.782 3.782 3.7823.774 3.774 3.774 3.7743.767 3.767 3.767 3.7673.686 3.686 3.686 3.6863.675 3.675 3.675 3.6753.666 3.666 3.666 3.6663.415 3.415 3.415 3.4153.405 3.405 3.405 3.4053.396 3.396 3.396 3.3962.945 2.945 2.945 2.945

1.763 1.763 1.763 1.763

O

N

O

O

3ia

CD

Cl 3

, 500

MH

z

O

OO

~ S79 ~

Page 80: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

188.379 188.379 188.379 188.379

164.571 164.571 164.571 164.571160.613 160.613 160.613 160.613159.583 159.583 159.583 159.583

136.891 136.891 136.891 136.891

132.771 132.771 132.771 132.771

128.020 128.020 128.020 128.020

118.396 118.396 118.396 118.396

113.427 113.427 113.427 113.427

107.351 107.351 107.351 107.351

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.699 66.699 66.699 66.699 66.603 66.603 66.603 66.603

46.306 46.306 46.306 46.306

41.785 41.785 41.785 41.785

25.894 25.894 25.894 25.894

O

N

O

O

3ia

CD

Cl 3

, 125

MH

z

O

OO

~ S80 ~

Page 81: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

1.00 1.00 1.00 1.00

1.05 1.05 1.05 1.05

1.03 1.03 1.03 1.03

8.13 8.13 8.13 8.13

6.26 6.26 6.26 6.26

7.980 7.980 7.980 7.980

7.657 7.657 7.657 7.6577.640 7.640 7.640 7.640

7.260 7.260 7.260 7.2607.020 7.020 7.020 7.0207.003 7.003 7.003 7.003

3.688 3.688 3.688 3.688

1.724 1.724 1.724 1.724

N

O 4ia

CD

Cl 3

, 500

MH

z

O

OO

O

~ S81 ~

Page 82: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

168.482 168.482 168.482 168.482

160.155 160.155 160.155 160.155156.988 156.988 156.988 156.988

135.747 135.747 135.747 135.747

129.594 129.594 129.594 129.594128.545 128.545 128.545 128.545

117.805 117.805 117.805 117.805

113.045 113.045 113.045 113.045

106.836 106.836 106.836 106.836

77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.699 66.699 66.699 66.699

48.347 48.347 48.347 48.347

42.776 42.776 42.776 42.776

25.732 25.732 25.732 25.732

N

O 4ia

CD

Cl 3

, 125

MH

z

O

OO

O

~ S82 ~

Page 83: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

0.93 0.93 0.93 0.93

1.00 1.00 1.00 1.000.99 0.99 0.99 0.99

4.28 4.28 4.28 4.282.17 2.17 2.17 2.172.12 2.12 2.12 2.12

8.235 8.235 8.235 8.2358.232 8.232 8.232 8.2328.229 8.229 8.229 8.2298.227 8.227 8.227 8.2277.575 7.575 7.575 7.5757.573 7.573 7.573 7.5737.565 7.565 7.565 7.5657.562 7.562 7.562 7.5627.373 7.373 7.373 7.3737.368 7.368 7.368 7.3687.363 7.363 7.363 7.3637.357 7.357 7.357 7.3577.260 7.260 7.260 7.260

3.773 3.773 3.773 3.7733.769 3.769 3.769 3.7693.765 3.765 3.765 3.7653.761 3.761 3.761 3.7613.758 3.758 3.758 3.7583.752 3.752 3.752 3.7523.740 3.740 3.740 3.7403.733 3.733 3.733 3.7333.730 3.730 3.730 3.7303.726 3.726 3.726 3.7263.722 3.722 3.722 3.7223.719 3.719 3.719 3.7193.657 3.657 3.657 3.6573.654 3.654 3.654 3.6543.648 3.648 3.648 3.6483.638 3.638 3.638 3.6383.434 3.434 3.434 3.4343.423 3.423 3.423 3.4233.414 3.414 3.414 3.414

O

N

O

O

3ja

CD

Cl 3

, 500

MH

z

S

~ S83 ~

Page 84: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

190.0

190.0

190.0

190.0

180.0

180.0

180.0

180.0

170.0

170.0

170.0

170.0

160.0

160.0

160.0

160.0

150.0

150.0

150.0

150.0

140.0

140.0

140.0

140.0

130.0

130.0

130.0

130.0

120.0

120.0

120.0

120.0

110.0

110.0

110.0

110.0

100.0

100.0

100.0

100.0

90.0

90.0

90.0

90.0

80.0

80.0

80.0

80.0

70.0

70.0

70.0

70.0

60.0

60.0

60.0

60.0

50.0

50.0

50.0

50.0

40.0

40.0

40.0

40.0

30.0

30.0

30.0

30.0

20.0

20.0

20.0

20.0

10.0

10.0

10.0

10.0

184.253 184.253 184.253 184.253

165.071 165.071 165.071 165.071

138.420 138.420 138.420 138.420136.684 136.684 136.684 136.684

127.250 127.250 127.250 127.250126.849 126.849 126.849 126.849

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.727 66.727 66.727 66.727 66.555 66.555 66.555 66.555

46.257 46.257 46.257 46.257

41.669 41.669 41.669 41.669

O

N

O

O

3ja

CD

Cl 3

, 125

MH

z

S

~ S84 ~

Page 85: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

1.00 1.00 1.00 1.00

1.03 1.03 1.03 1.031.01 1.01 1.01 1.01

9.05 9.05 9.05 9.05

7.525 7.525 7.525 7.5257.522 7.522 7.522 7.5227.519 7.519 7.519 7.5197.517 7.517 7.517 7.5177.350 7.350 7.350 7.3507.345 7.345 7.345 7.3457.341 7.341 7.341 7.3417.334 7.334 7.334 7.3347.260 7.260 7.260 7.2607.181 7.181 7.181 7.1817.179 7.179 7.179 7.1797.171 7.171 7.171 7.1717.168 7.168 7.168 7.168

3.694 3.694 3.694 3.694

O

N

O

4ja

CD

Cl 3

, 500

MH

z

S

~ S85 ~

Page 86: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

165.735 165.735 165.735 165.735

135.851 135.851 135.851 135.851

126.905 126.905 126.905 126.905126.628 126.628 126.628 126.628126.103 126.103 126.103 126.103

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.752 76.752 76.752 76.752

66.823 66.823 66.823 66.823

47.908 47.908 47.908 47.908

42.681 42.681 42.681 42.681

O

N

O

4ja

CD

Cl 3

, 125

MH

z

S

~ S86 ~

Page 87: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

1.00 1.00 1.00 1.00

1.04 1.04 1.04 1.04

1.04 1.04 1.04 1.04

1.01 1.01 1.01 1.01

1.02 1.02 1.02 1.02

7.34 7.34 7.34 7.34

2.14 2.14 2.14 2.14

2.08 2.08 2.08 2.08

8.212 8.212 8.212 8.2128.209 8.209 8.209 8.2097.834 7.834 7.834 7.8347.830 7.830 7.830 7.8307.817 7.817 7.817 7.8177.813 7.813 7.813 7.8137.350 7.350 7.350 7.3507.333 7.333 7.333 7.3337.260 7.260 7.260 7.2607.119 7.119 7.119 7.1197.113 7.113 7.113 7.113

6.587 6.587 6.587 6.5876.582 6.582 6.582 6.5826.580 6.580 6.580 6.580

3.780 3.780 3.780 3.7803.775 3.775 3.775 3.7753.634 3.634 3.634 3.6343.607 3.607 3.607 3.6073.602 3.602 3.602 3.6023.598 3.598 3.598 3.5983.587 3.587 3.587 3.5873.368 3.368 3.368 3.3683.358 3.358 3.358 3.3583.349 3.349 3.349 3.349

O

N

O

O

3ka

CD

Cl 3

, 500

MH

z

NM

e

~ S87 ~

Page 88: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

191.517 191.517 191.517 191.517

166.393 166.393 166.393 166.393

139.867 139.867 139.867 139.867

131.006 131.006 131.006 131.006128.011 128.011 128.011 128.011125.264 125.264 125.264 125.264124.835 124.835 124.835 124.835122.097 122.097 122.097 122.097

109.783 109.783 109.783 109.783

103.326 103.326 103.326 103.326

77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.575 66.575 66.575 66.575 66.508 66.508 66.508 66.508

46.153 46.153 46.153 46.153

41.308 41.308 41.308 41.308

32.942 32.942 32.942 32.942

O

N

O

O

3ka

CD

Cl 3

, 125

MH

z

NM

e

~ S88 ~

Page 89: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

1.01 1.01 1.01 1.01

2.10 2.10 2.10 2.10

1.00 1.00 1.00 1.00

1.02 1.02 1.02 1.02

11.79 11.79 11.79 11.79

7.697 7.697 7.697 7.6977.316 7.316 7.316 7.3167.300 7.300 7.300 7.3007.290 7.290 7.290 7.2907.287 7.287 7.287 7.2877.274 7.274 7.274 7.2747.270 7.270 7.270 7.2707.260 7.260 7.260 7.2607.082 7.082 7.082 7.0827.077 7.077 7.077 7.0776.503 6.503 6.503 6.5036.496 6.496 6.496 6.496

3.763 3.763 3.763 3.7633.679 3.679 3.679 3.679

N

O 4ka

CD

Cl 3

, 500

MH

z

NM

e

O

~ S89 ~

Page 90: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

171.744 171.744 171.744 171.744

137.072 137.072 137.072 137.072

129.938 129.938 129.938 129.938127.687 127.687 127.687 127.687125.951 125.951 125.951 125.951120.857 120.857 120.857 120.857120.390 120.390 120.390 120.390

109.011 109.011 109.011 109.011

101.523 101.523 101.523 101.523

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.804 66.804 66.804 66.804

48.223 48.223 48.223 48.223

43.015 43.015 43.015 43.015

32.761 32.761 32.761 32.761

N

O 4ka

CD

Cl 3

, 125

MH

z

NM

e

O

~ S90 ~

Page 91: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

1.00 1.00 1.00 1.00

1.02 1.02 1.02 1.021.03 1.03 1.03 1.03 1.02 1.02 1.02 1.020.99 0.99 0.99 0.99

1.03 1.03 1.03 1.03

4.14 4.14 4.14 4.14

2.11 2.11 2.11 2.11

2.05 2.05 2.05 2.05

9.024 9.024 9.024 9.0249.020 9.020 9.020 9.0209.015 9.015 9.015 9.0159.012 9.012 9.012 9.0128.448 8.448 8.448 8.4488.444 8.444 8.444 8.4448.279 8.279 8.279 8.2798.277 8.277 8.277 8.2778.263 8.263 8.263 8.2638.260 8.260 8.260 8.2608.237 8.237 8.237 8.2378.233 8.233 8.233 8.2338.220 8.220 8.220 8.2208.216 8.216 8.216 8.2168.183 8.183 8.183 8.1838.166 8.166 8.166 8.1667.497 7.497 7.497 7.4977.489 7.489 7.489 7.4897.481 7.481 7.481 7.4817.473 7.473 7.473 7.4737.260 7.260 7.260 7.260

3.806 3.806 3.806 3.8063.657 3.657 3.657 3.6573.648 3.648 3.648 3.6483.638 3.638 3.638 3.6383.417 3.417 3.417 3.4173.406 3.406 3.406 3.4063.397 3.397 3.397 3.397

ON

O

O

3la

CD

Cl 3

, 500

MH

z

N

~ S91 ~

Page 92: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

190.258 190.258 190.258 190.258

165.001 165.001 165.001 165.001

153.412 153.412 153.412 153.412150.655 150.655 150.655 150.655

137.683 137.683 137.683 137.683132.637 132.637 132.637 132.637130.748 130.748 130.748 130.748127.410 127.410 127.410 127.410127.372 127.372 127.372 127.372122.259 122.259 122.259 122.259

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.651 66.651 66.651 66.651 66.565 66.565 66.565 66.565

46.268 46.268 46.268 46.268

41.689 41.689 41.689 41.689

ON

O

O

3la

CD

Cl 3

, 125

MH

z

N

~ S92 ~

Page 93: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.00

10.00

10.00

10.009.50

9.50

9.50

9.509.00

9.00

9.00

9.008.50

8.50

8.50

8.508.00

8.00

8.00

8.007.50

7.50

7.50

7.507.00

7.00

7.00

7.006.50

6.50

6.50

6.506.00

6.00

6.00

6.005.50

5.50

5.50

5.505.00

5.00

5.00

5.004.50

4.50

4.50

4.504.00

4.00

4.00

4.003.50

3.50

3.50

3.503.00

3.00

3.00

3.002.50

2.50

2.50

2.502.00

2.00

2.00

2.001.50

1.50

1.50

1.501.00

1.00

1.00

1.000.50

0.50

0.50

0.500.00

0.00

0.00

0.00-0.50

-0.50

-0.50

-0.50

1.00 1.00 1.00 1.00

2.17 2.17 2.17 2.17

1.07 1.07 1.07 1.07

1.11 1.11 1.11 1.11

1.06 1.06 1.06 1.06

8.93 8.93 8.93 8.93

8.989 8.989 8.989 8.989

8.214 8.214 8.214 8.2148.198 8.198 8.198 8.1988.169 8.169 8.169 8.1698.152 8.152 8.152 8.1527.930 7.930 7.930 7.9307.736 7.736 7.736 7.7367.733 7.733 7.733 7.7337.719 7.719 7.719 7.7197.716 7.716 7.716 7.7167.484 7.484 7.484 7.4847.476 7.476 7.476 7.4767.260 7.260 7.260 7.260

3.819 3.819 3.819 3.8193.660 3.660 3.660 3.6603.499 3.499 3.499 3.499

N

O 4la

CD

Cl 3

, 500

MH

zON

~ S93 ~

Page 94: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

169.674 169.674 169.674 169.674

151.647 151.647 151.647 151.647148.404 148.404 148.404 148.404

136.471 136.471 136.471 136.471133.419 133.419 133.419 133.419130.033 130.033 130.033 130.033127.782 127.782 127.782 127.782127.095 127.095 127.095 127.095121.964 121.964 121.964 121.964

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

66.870 66.870 66.870 66.870

48.318 48.318 48.318 48.318

42.662 42.662 42.662 42.662

N

O 4la

CD

Cl 3

, 12

5 M

HzO

N

~ S94 ~

Page 95: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.0

10.0

10.0

10.0

9.59.59.59.5

9.09.09.09.0

8.58.58.58.5

8.08.08.08.0

7.57.57.57.5

7.07.07.07.0

6.56.56.56.5

6.06.06.06.0

5.55.55.55.5

5.05.05.05.0

4.54.54.54.5

4.04.04.04.0

3.53.53.53.5

3.03.03.03.0

2.52.52.52.5

2.02.02.02.0

1.51.51.51.5

1.01.01.01.0

0.50.50.50.5

0.00.00.00.0

-0.5

-0.5

-0.5

-0.5

1.00 1.00 1.00 1.00

4.08 4.08 4.08 4.08

7.15 7.15 7.15 7.15

8.29 8.29 8.29 8.29

8.453 8.453 8.453 8.4538.006 8.006 8.006 8.0067.984 7.984 7.984 7.9847.968 7.968 7.968 7.9687.906 7.906 7.906 7.9067.890 7.890 7.890 7.8907.661 7.661 7.661 7.6617.646 7.646 7.646 7.6467.602 7.602 7.602 7.6027.589 7.589 7.589 7.5897.409 7.409 7.409 7.4097.260 7.260 7.260 7.260

3.818 3.818 3.818 3.818

3.627 3.627 3.627 3.6273.465 3.465 3.465 3.465

ON

O

NB

z

3ml

CD

Cl 3

, 500

MH

z

~ S95 ~

Page 96: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

190.993 190.993 190.993 190.993

170.590 170.590 170.590 170.590

165.649 165.649 165.649 165.649

136.367 136.367 136.367 136.367134.755 134.755 134.755 134.755133.057 133.057 133.057 133.057132.284 132.284 132.284 132.284130.157 130.157 130.157 130.157129.823 129.823 129.823 129.823129.575 129.575 129.575 129.575129.184 129.184 129.184 129.184128.612 128.612 128.612 128.612127.906 127.906 127.906 127.906127.219 127.219 127.219 127.219126.971 126.971 126.971 126.971123.413 123.413 123.413 123.413

77.248 77.248 77.248 77.248 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

47.231 47.231 47.231 47.231 45.886 45.886 45.886 45.886 42.013 42.013 42.013 42.013 41.422 41.422 41.422 41.422

ON

O

NB

z

3ml

CD

Cl 3

, 12

5 M

Hz

~ S96 ~

Page 97: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

10.0

10.0

10.0

10.0

9.59.59.59.5

9.09.09.09.0

8.58.58.58.5

8.08.08.08.0

7.57.57.57.5

7.07.07.07.0

6.56.56.56.5

6.06.06.06.0

5.55.55.55.5

5.05.05.05.0

4.54.54.54.5

4.04.04.04.0

3.53.53.53.5

3.03.03.03.0

2.52.52.52.5

2.02.02.02.0

1.51.51.51.5

1.01.01.01.0

0.50.50.50.5

0.00.00.00.0

-0.5

-0.5

-0.5

-0.5

4.00 4.00 4.00 4.00

7.99 7.99 7.99 7.99

7.97 7.97 7.97 7.97

7.920 7.920 7.920 7.9207.870 7.870 7.870 7.8707.550 7.550 7.550 7.5507.543 7.543 7.543 7.5437.535 7.535 7.535 7.5357.496 7.496 7.496 7.4967.479 7.479 7.479 7.4797.416 7.416 7.416 7.416

3.771 3.771 3.771 3.771

3.576 3.576 3.576 3.576

N

O 4ml

CD

Cl 3

, 500

MH

zNB

z

~ S97 ~

Page 98: Royal Society of Chemistry · 2015. 2. 27. · 13C NMR spectroscopy was recorded on JEOL ECA500 (125 MHz) NMR spectrometer. Chemical shifts are reported in ppm from the solvent as

PPM

PPM

PPM

PPM

200

200

200

200

190

190

190

190

180

180

180

180

170

170

170

170

160

160

160

160

150

150

150

150

140

140

140

140

130

130

130

130

120

120

120

120

110

110

110

110

100

100

100

100

90

9090

90

80

8080

80

70

7070

70

60

6060

60

50

5050

50

40

4040

40

30

3030

30

20

2020

20

10

1010

10

0 000

170.638 170.638 170.638 170.638170.609 170.609 170.609 170.609

135.060 135.060 135.060 135.060133.743 133.743 133.743 133.743132.589 132.589 132.589 132.589132.303 132.303 132.303 132.303130.052 130.052 130.052 130.052128.593 128.593 128.593 128.593128.488 128.488 128.488 128.488128.354 128.354 128.354 128.354127.772 127.772 127.772 127.772127.286 127.286 127.286 127.286127.067 127.067 127.067 127.067127.009 127.009 127.009 127.009126.847 126.847 126.847 126.847124.024 124.024 124.024 124.024

77.258 77.258 77.258 77.258 77.000 77.000 77.000 77.000 76.742 76.742 76.742 76.742

47.670 47.670 47.670 47.670

42.462 42.462 42.462 42.462

N

O 4ml

CD

Cl 3

, 125

MH

zNB

z

~ S98 ~