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Supplementary Material
RhCl3amine-catalyzed [2+2+2] cyclization of alkynes
Kenta Yoshida Ichiro Morimoto Koichi Mitsudo Hideo Tanaka
General 1H and 13C NMR spectra were recorded on Varian INOVA UNITY 600 (1H 600 MHz 13C 150 MHz) spectrometers in CDCl3 using TMS or residual chloroform as internal standard Splitting patterns are designated as s singlet d doublet t triplet q quartet m multiplet dd double doublet and tt triple triplet Coupling constants are reported in hertz (Hz) IR spectra were recorded on a JASCO FTIR-4100 spectrophotometer in wave number (cmndash1) and only major absorption bands are compiled Analytic thin layer chromatography (TLC) was performed on Merck pre-coated plate silica gel 60 F254 (025 mm thickness) Column chromatography was performed on KANTO CHEMICAL silica gel 60N (40ndash50 μm) Preparative recycling gel permeation chromatography (GPC) was performed with a JAI LC-9101 instrument equipped with JAIGEL-1HJAIGEL-2H column using chloroform as an eluent Elemental analysis was obtained with Perkin-Elmer PE 2400 Series II CHNSO analyzer Unless otherwise noted all materials were obtained from commercial suppliers and used without further purification Diynes 4a and 4b were prepared according to literature procedures1 All reactions were performed in dry solvents under argon atmosphere Toluene benzene xylene 14-dioxane i-PrOH CH3CN 12-dichloroethane CH2Cl2 hexane and heptane were distilled from CaH2 DME THF Et2O and EtOH were distilled from sodium benzophenone ketyl under argon
General procedure for Rhamine-catalyzed cyclotrimerization of internal alkyne To a suspension of RhCl3bull3H2O (10 mg 004 mmol) in toluene (30 mL) were added i-Pr2NEt (26 μL 015 mmol) and ethyl phenylpropiolate 1a (87 mg 050 mmol) The mixture was stirred at reflux for 24 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford 124-triethoxycarbonyl-356-triphenylbenzene 2a (79 mg 91) as colorless solids 124-Triethoxycarbonyl-356-triphenylbenzene (2a)2
Colorless solids Rf = 020 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 068 (t J = 72 Hz 3H) 087 (t J = 72 Hz 3H) 090 (t J = 72 Hz 3H) 365 (q J = 72 Hz 2H) 394 (q J = 72 Hz 2H) 398 (q J = 72 Hz 2H) 700ndash704 (m 4H) 711ndash714 (m 6H) 735 (s 5H) 13C NMR (150 MHz CDCl3)δ 133 1341 1343 609 6150 6151 1271 1273 1274 1275 1279 1280 1289 1298 1299 1320 1341 1372 1373 1374 1376 1392 1407 16729 16733 1677 IR (KBr) 3057 2981 2936 1729 1232 1200 cmndash1 Anal Calcd for C33H30O6 C 7584 H 579 Found C 7561 H 582
In a similar manner the Rhamine-catalyzed cyclotrimerization of internal alkynes 1bndash1g was carried out The reaction conditions and the results are illustrated in Table 5 124-Trimethoxycarbonyl-356-triphenylbenzene (2b)2 Colorless solids Rf = 031 (hexaneEtOAc 11) 1H NMR (600 MHz CDCl3) δ 317 (s 3H) 347 (s 3H) 351 (s 3H) 700ndash703 (m 4H) 712ndash715 (m 6H) 732ndash738 (m 6H) 13C NMR (150 MHz CDCl3)δ 517 523 524 1272 1274 12751 12752 1280 1281 1285 12957 12963 1317 1341 1371 13720 13723 1373 1392 1409 1677 1679 1681 IR (KBr) 3030 3001 2951 1744 1735 1244 1205 cmndash1 124-Trimethyl-356-triphenylbenzene (2c)3 Colorless solids Rf = 055 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 172 (s 3H) 204 (s 3H) 205 (s 3H) 696ndash714 (m 10H) 725 (dd J = 78 12 Hz 2H) 735 (tt J = 78 12 Hz 1H) 745 (tm J = 78 Hz 1H) 13C NMR (150 MHz CDCl3) δ181 183 194 1256 1257 1265 12728 12731 1284 1294 130286 130294 1313 1319 1339 1392 1406 1414 14158 14161 1424 IR (KBr) 3055 2956 2918 2849 cmndash1 124-Triethoxycarbonyl-356-trimethylbenzene (2d)4 Colorless liquid Rf = 013 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ135 (t J = 72 Hz 3H) 136 (t J = 72 Hz 3H) 138 (t J = 72 Hz 3H) 222 (s 3H) 226 (s 3H) 230 (s 3H) 432 (q J = 72 Hz 2H) 433 (q J = 72 Hz 2H) 440 (q J = 72 Hz 2H) 13C NMR (150 MHz CDCl3) δ140 142 165 170 173 6137 6146 6149 1299 1303 1326 1337 1358 1375 1678 1685 1694 IR (neat) 2982 2938 2906 1731 1576 cmndash1 Anal Calcd for C18H24O6 C 6427 H 719 Found C 6402 H 713 135-Triethoxycarbonyl-246-trimethylbenzene (3d)4 Colorless liquid Rf = 020 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ137 (t J = 72 Hz 9H) 223 (s 9H) 438 (q J = 72 Hz 6H) 13C NMR (150 MHz CDCl3) δ 142 171 613 1321 1335 1690 IR (neat) 2981 2937 1728 1581 1226 cmndash1 Anal Calcd for C18H24O6 C 6427 H 719 Found C 6434 H 729 Hexapropylbenzene (2e)5
Colorless solids Rf = 080 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 104 (t J = 72 Hz 18H) 149ndash157 (m 12H) 246ndash248 (m 12H) 13C NMR (150 MHz CDCl3) δ 153 248 322 1367 IR (KBr) 2952 2928 2890 2869 cmndash1 Anal Calcd for C24H42 C 8719 H 1281 Found C 8721 H 1314
Hexaphenylbenzene (2f)3
Colorless solids Rf = 050 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 683ndash686 (m 30H) 13C NMR (150 MHz CDCl3) δ 1252 1265 1314 1403 1406 IR (KBr) 3056 3024 2925 cmndash1 Hexamethoxycarbonylbenzene (2g)
Colorless solids Rf = 031 (hexaneEtOAc 11) 1H NMR (600 MHz CDCl3) δ 388 (s 18H) 13C NMR (150 MHz CDCl3) δ 535 1339 1651 IR (KBr) 3009 2958 1739 1445 cmminus1 Anal Calcd for C18H18O6 C 5071 H 426 Found C 5077 H 399 General procedure for Rhamine-catalyzed cyclotrimerization of di(thienyl)acetylene To a solution of RhCl33H2O (11 mg 004 mmol) in i-PrOH (30 mL) were added i-Pr2NEt (26 μL 015 mmol) and di(2-thienyl)acetylene 1h (96 mg 050 mmol) The mixture was stirred at reflux for 24 h After being cooled to room temperature the reaction mixture was filtered and concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexanetoluene 51) to afford hexa(2-thienyl)benzene 2h (47 mg 49) as yellow solids Hexa(2-thienyl)benzene (2h) Yellow solids Rf = 027 (hexanetoluene 51) 1H NMR (600 MHz CDCl3) δ 659 (dd J = 36 12 Hz 6H) 668 (dd J = 54 36 Hz 6H) 708 (dd J = 54 12 Hz 6H) 13C NMR (150 MHz CDCl3) δ 1258 1262 1291 1370 1407 IR (KBr) 3068 2923 2360 1647 1381 694 cmminus1 Anal Calcd for C30H18S6 C 6312 H 318 Found C 6308 H 336 In a similar manner the Rhamine-catalyzed cyclotrimerization of di(thienyl)acetylene derivatives 1indash1k was carried out The reaction conditions and the results are illustrated in Table 5 Hexakis(5-methyl-2-thienyl)benzene (2i) Yellow solids Rf = 023 (hexanetoluene 51) 1H NMR (600 MHz CDCl3) δ 633 (s 12H) 230 (s 18H) 13C NMR (150 MHz CDCl3) δ 152 1239 1287 1370 1388 1402 IR (KBr) 3068 2912 2855 2357 1747 1442 1219 800 cmminus1 Anal Calcd for C36H30S6 C 6601 H 462 Found C 6609 H 453 Hexakis(5-acetyl-2-thienyl)benzene (2j) Colorless solids Rf = 007 (hexaneEtOAc 31) 1H NMR (600 MHz CDCl3) δ 727 (d J = 36 Hz 6H) 667 (d J = 36 Hz 6H) 243 (s 18H) 13C NMR (150 MHz CDCl3) δ 267 1309 1318 1365 1458 1467 1907 IR (KBr) 3080 1658 1471 1381 1274 cmminus1
434 Hexa(3-thienyl)benzene (2k) Brown solids Rf = 027 (hexaneEtOAc 31) 1H NMR (600 MHz CDCl3) δ 691 (dd J = 48 30 Hz 6H) 658 (dd J = 30 15 Hz 6H) 650 (dd J = 48 36 Hz 6H) 13C NMR (150 MHz CDCl3) δ 1233 1241 1297 1365 1403 IR (KBr) 3068 2923 2360 1647 1381 1223 694 cmminus1 Anal Calcd for C30H18S6 C 6312 H 318 Found C 6308 H 336 General procedure for Rhamine-catalyzed cyclotrimerization of terminal alkyne To a suspension of RhCl3bull3H2O (11 mg 004 mmol) in toluene (30 mL) were added i-Pr2NEt (26 μL 015 mmol) and phenylacetylene 1l (55 mg 050 mmol) The mixture was stirred at reflux for 12 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford 124-triphenylbenzene 2l (54 mg 98) as colorless solids 124-Triphenylbenzene (2l)67
Colorless solids Rf = 057 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 717ndash724 (m 10H) 737 (tt J = 78 12 Hz 1H) 745ndash748 (m 2H) 751 (dd J = 78 12 Hz 1H) 765ndash769 (m 4H) 13C NMR (150 MHz CDCl3) δ 1261 1265 1266 1271 1274 12789 12792 1288 1294 12987 12990 1311 1395 1404 1406 1410 1411 1415 IR (KBr) 3075 3056 3027 cmndash1 In a similar manner the Rhamine-catalyzed cyclotrimerization of terminal alkynes 1mndash1o was conducted The reaction conditions and the results are illustrated in Table 5 124-Tris(4-methylphenyl)benzene (2m)58 Colorless solids Rf = 060 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 232 (s 3H) 233 (s 3H) 240 (s 3H) 703ndash710 (m 8H) 726 (dd J = 78 06 Hz 2H) 746 (dd J = 78 06 Hz 1H) 756ndash762 (m 4H) 13C NMR (150 MHz CDCl3) δ 2111 2113 1257 1269 1286 1287 1292 1295 12968 12971 1311 1360 1361 1371 1378 1383 1387 1391 1400 1408 IR (KBr) 3025 2917 2863 cmndash1 Anal Calcd for C27H24 C 9306 H 694 Found C 9267 H 733 124-Trihexylbenzene (2n)5
Colorless liquid Rf = 077 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 087ndash091 (m 9H) 128ndash139 (m 18H) 154ndash159 (m 6H) 252ndash258 (m 6H) 692 (dd J = 78 18 Hz 1H) 695 (d J = 18 Hz 1H) 704 (d J = 78 Hz 1H) 124-Triethoxycarbonylbenzene (2o)9 Yellow liquid Rf = 023 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 138 (t J = 72 Hz 3H) 139 (t J = 72 Hz 3H) 141 (t J = 72 Hz 3H) 439 (q J = 72 Hz 4H) 441 (q J = 72 Hz 2H)
776 (dd J = 84 06 Hz 1H) 819 (dd J = 84 12 Hz 1H) 840 (dd J = 12 06 Hz 1H) 13C NMR (150 MHz CDCl3) δ 140 141 142 617 619 620 1288 1301 13200 13204 1327 1362 1650 1666 1672 IR (neat) 2983 2938 1727 1244 cmndash1 Anal Calcd for C15H18O6 C 6122 H 616 Found C 6114 H 660 135-Triethoxycarbonylbenzene (3o)10
Colorless solids Rf = 023 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 143 (t J = 72 Hz 9H) 444 (q J = 72 Hz 6H) 885 (s 3H) 13C NMR (150 MHz CDCl3) δ 143 617 1314 1344 1651 IR (KBr) 2943 2907 2877 1724 1240 cmndash1 Anal Calcd for C15H18O6 C 6122 H 616 Found C 6146 H 628 Synthesis of RhCl3bull3H2Oi-Pr2NEt complex To a solution of RhCl3bull3H2O (26 mg 01 mmol) in i-PrOH (6 mL) was added i-Pr2NEt (51 μL 03 mmol) The mixture was stirred at room temperature (or reflux) for 05 h and was oncentrated under reduced pressure The residue was purified by gel permeation chromatography Then the solid was purified by recyclization and colorless crystals were obtained General Procedure for Cyclization of Diyne 4a and Alkyne 1 To a solution of RhCl3bull3H2O (11 mg 004 mmol) and i-Pr2NEt (26 μL 015 mmol) in i-PrOH (20 mL) were added phenylacetylene 1l (217 mg 20 mmol) and diyne 4a (116 mg 049 mmol) in i-PrOH (30 mL) The mixture was stirred at reflux for 2 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford diethyl 5-phenyl-1H-indene-22(3H)-dicarboxylate 5al (138 mg 81) as yellow liquid Diethyl 5-Phenyl-1H-indene-22(3H)-dicarboxylate (5al)11
Yellow liquid Rf = 037 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 125ndash128 (m 6H) 363 (s 2H) 366 (s 2H) 426 (q J = 72 Hz 4H) 726ndash727 (m 1H) 732ndash734 (m 1H) 739ndash743 (m 4H) 755ndash756 (m 2H) 13C NMR (150 MHz CDCl3) δ 140 402 404 605 617 1230 1244 1261 1270 1271 1286 1391 1403 1407 1413 1716 IR (neat) 3031 2980 2936 1733 cmndash1 Anal Calcd for C21H22O4 C 7454 H 656 Found C 7453 H 674 In a similar manner the Rhamine-catalyzed cyclotrimerization of diyne 4a and alkynes 1a 1c 1f and 1n was carried out The reaction conditions and the results are illustrated in Table 6 Diethyl 5-Hexyl-1H-indene-22(3H)-dicarboxylate (5an)4
Orange liquid Rf = 047 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 087ndash089 (m 3H)
124ndash133 (m 12H) 154ndash160 (m 2H) 254 (t J = 72 Hz 2H) 355 (s 2H) 356 (s 2H) 420 (q J = 72 Hz 4H) 697 (d J = 72 Hz 1H) 701 (s 1H) 708 (d J = 72 Hz 1H) 13C NMR (150 MHz CDCl3) δ 140 141 226 290 3169 3172 358 401 404 605 616 1238 1241 1271 1371 1400 1418 1718 IR (neat) 2957 2928 2856 1735 cmndash1 Anal Calcd for C21H30O4 C 7280 H 873 Found C 7279 H 884 Diethyl 5-Ethoxycarbonyl 6-Phenyl-1H-indene-22(3H)-dicarboxylate (5aa) Colorless solids Rf = 026 (hexaneEtOAc 41) 1H NMR (600 MHz CDCl3) δ 096 (t J = 72 Hz 3H) 127 (t J = 72 Hz 6H) 363 (s 2H) 365 (s 2H) 404 (q J = 72 Hz 2H) 422 (q J = 72 Hz 2H) 719 (d J = 06 Hz 1H) 726ndash728 (m 2H) 730ndash737 (m 2H) 766 (s 1H) 13C NMR (150 MHz CDCl3) δ 136 140 400 404 604 608 618 1255 1264 1269 1279 1283 1302 1392 14166 14174 1437 1688 1713 IR (KBr) 3059 3024 2980 2935 2905 1732 cmndash1 Anal Calcd for C24H26O6 C 7023 H 638 Found C 7015 H 644 Diethyl 5-Methyl 6-Phenyl-1H-indene-22(3H)-dicarboxylate (5ac) Yellow liquid Rf = 040 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 127 (t J = 72 Hz 6H) 221 (s 3H) 359 (s 2H) 360 (s 2H) 422 (q J = 72 Hz 4H) 705 (s 1H) 710 (s 1H) 728ndash733 (m 3H) 737ndash740 (m 2H) 13C NMR (150 MHz CDCl3) δ 140 204 402 403 605 617 1255 1266 1280 1292 1341 1375 1391 1408 1421 1717 IR (neat) 3057 2980 2935 1733 1244 cmndash1 Anal Calcd for C22H24O4 C 7498 H 686 Found C 7493 H 699 Diethyl 56-Diphenyl-1H-indene-22(3H)-dicarboxylate (5af) Colorless solids Rf = 039 (hexaneEtOAc 41) 1H NMR (600 MHz CDCl3) δ 1281 (t J = 72 Hz 3H) 1282 (t J = 72 Hz 3H) 368 (s 4H) 4240 (q J = 72 Hz 2H) 4241 (q J = 72 Hz 2H) 709ndash711 (m 4H) 715ndash720 (m 6H) 725 (d J = 06 Hz 2H) 13C NMR (150 MHz CDCl3) δ 140 403 605 618 1263 1278 1299 1394 1396 1416 1717 IR (KBr) 3057 2985 2903 1732 1708 cmndash1 General Procedure for Cyclization of Diyne 4b and Alkyne 1f To a solution of RhCl3bull3H2O (11 mg 004 mmol) and i-Pr2NEt (26 μL 015 mmol) in i-PrOH (20 mL) were added diphenylacetylene 1f (900 mg 50 mmol) and diyne 4b (132 mg 050 mmol) in i-PrOH (30 mL) The mixture was stirred at reflux for 24 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford 47-dimethyl-56-diphenyl-indan-22-dicarboxylic acid diethyl ester 5bf (102 mg 46) and 45 of 4b was recovered
Diethyl 47-Dimethyl-56-diphenyl-1H-indene-22(3H)-dicarboxylate (5bf) Red liquid Rf = 050 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 132 (t J = 72 Hz 6H) 200 (s 6H) 369 (s 4H) 428 (q J = 72 Hz 4H) 692 (d J = 72 Hz 4H) 704ndash706 (m 2H) 710ndash712 (m 4H) 13C NMR (150 MHz CDCl3) δ 137 192 307 644 1182 1280 1288 1302 1344 1445 1671 IR (neat) 3056 3021 2981 2935 1733 1242 cmndash1 Reference 1 Bhar S Chaudhuri K S Sahu S G Panja C Tetrahedron 2001 57 9011ndash9016 2 Diercks R tom Dieck H Z Naturforsch B Chem Sc 1984 39B 180ndash184 3 Sigman M S Fatland A W Eaton B E J Am Chem Soc 1998 120 5130ndash5131 4 Mori N Ikeda S Odashima K Chem Commun 2001 181ndash182 5 Li J Jiang H Chen M J Org Chem 2001 66 3627ndash3629 6 Rodriacuteguez J G Lafuente A Martiacuten-Villamil R J Polym Sci Part A Polym Chem 2005 43 1228ndash1237 7 Yasuda M Kojima R Tsutsui H Utsunomiya D Ishii K Jinnouchi K Shiragami T J Org Chem 2003 68 7618ndash7624 8 Tagliatesta P Floris B Galloni P Leoni A DrsquoArcangelo G Inorg Chem 2003 42 7701ndash7703 9 Tanaka K Toyoda K Wada A Shirasaki K Hirano M Chem Eur J 2005 11 1145ndash1156 10 Kanner C B Pandit U K Tetrahedron 1982 38 3597ndash3604 11 Hilt G Vogler T Hess W Galbiati F Chem Commun 2005 1474ndash1475
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PhCO2EtEtO2C
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PhCO2MeMeO2C
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2b
PhPh
PhCO2MeMeO2C
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2b
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PhMeMe
Me
2c
PhPh
PhMeMe
Me
2c
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MeCO2EtEtO2C
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CO2MeCO2MeMeO2C
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2g
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CO2MeCO2MeMeO2C
MeO2C
2g
2h
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S
SS
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2h
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2i
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In a similar manner the Rhamine-catalyzed cyclotrimerization of internal alkynes 1bndash1g was carried out The reaction conditions and the results are illustrated in Table 5 124-Trimethoxycarbonyl-356-triphenylbenzene (2b)2 Colorless solids Rf = 031 (hexaneEtOAc 11) 1H NMR (600 MHz CDCl3) δ 317 (s 3H) 347 (s 3H) 351 (s 3H) 700ndash703 (m 4H) 712ndash715 (m 6H) 732ndash738 (m 6H) 13C NMR (150 MHz CDCl3)δ 517 523 524 1272 1274 12751 12752 1280 1281 1285 12957 12963 1317 1341 1371 13720 13723 1373 1392 1409 1677 1679 1681 IR (KBr) 3030 3001 2951 1744 1735 1244 1205 cmndash1 124-Trimethyl-356-triphenylbenzene (2c)3 Colorless solids Rf = 055 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 172 (s 3H) 204 (s 3H) 205 (s 3H) 696ndash714 (m 10H) 725 (dd J = 78 12 Hz 2H) 735 (tt J = 78 12 Hz 1H) 745 (tm J = 78 Hz 1H) 13C NMR (150 MHz CDCl3) δ181 183 194 1256 1257 1265 12728 12731 1284 1294 130286 130294 1313 1319 1339 1392 1406 1414 14158 14161 1424 IR (KBr) 3055 2956 2918 2849 cmndash1 124-Triethoxycarbonyl-356-trimethylbenzene (2d)4 Colorless liquid Rf = 013 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ135 (t J = 72 Hz 3H) 136 (t J = 72 Hz 3H) 138 (t J = 72 Hz 3H) 222 (s 3H) 226 (s 3H) 230 (s 3H) 432 (q J = 72 Hz 2H) 433 (q J = 72 Hz 2H) 440 (q J = 72 Hz 2H) 13C NMR (150 MHz CDCl3) δ140 142 165 170 173 6137 6146 6149 1299 1303 1326 1337 1358 1375 1678 1685 1694 IR (neat) 2982 2938 2906 1731 1576 cmndash1 Anal Calcd for C18H24O6 C 6427 H 719 Found C 6402 H 713 135-Triethoxycarbonyl-246-trimethylbenzene (3d)4 Colorless liquid Rf = 020 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ137 (t J = 72 Hz 9H) 223 (s 9H) 438 (q J = 72 Hz 6H) 13C NMR (150 MHz CDCl3) δ 142 171 613 1321 1335 1690 IR (neat) 2981 2937 1728 1581 1226 cmndash1 Anal Calcd for C18H24O6 C 6427 H 719 Found C 6434 H 729 Hexapropylbenzene (2e)5
Colorless solids Rf = 080 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 104 (t J = 72 Hz 18H) 149ndash157 (m 12H) 246ndash248 (m 12H) 13C NMR (150 MHz CDCl3) δ 153 248 322 1367 IR (KBr) 2952 2928 2890 2869 cmndash1 Anal Calcd for C24H42 C 8719 H 1281 Found C 8721 H 1314
Hexaphenylbenzene (2f)3
Colorless solids Rf = 050 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 683ndash686 (m 30H) 13C NMR (150 MHz CDCl3) δ 1252 1265 1314 1403 1406 IR (KBr) 3056 3024 2925 cmndash1 Hexamethoxycarbonylbenzene (2g)
Colorless solids Rf = 031 (hexaneEtOAc 11) 1H NMR (600 MHz CDCl3) δ 388 (s 18H) 13C NMR (150 MHz CDCl3) δ 535 1339 1651 IR (KBr) 3009 2958 1739 1445 cmminus1 Anal Calcd for C18H18O6 C 5071 H 426 Found C 5077 H 399 General procedure for Rhamine-catalyzed cyclotrimerization of di(thienyl)acetylene To a solution of RhCl33H2O (11 mg 004 mmol) in i-PrOH (30 mL) were added i-Pr2NEt (26 μL 015 mmol) and di(2-thienyl)acetylene 1h (96 mg 050 mmol) The mixture was stirred at reflux for 24 h After being cooled to room temperature the reaction mixture was filtered and concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexanetoluene 51) to afford hexa(2-thienyl)benzene 2h (47 mg 49) as yellow solids Hexa(2-thienyl)benzene (2h) Yellow solids Rf = 027 (hexanetoluene 51) 1H NMR (600 MHz CDCl3) δ 659 (dd J = 36 12 Hz 6H) 668 (dd J = 54 36 Hz 6H) 708 (dd J = 54 12 Hz 6H) 13C NMR (150 MHz CDCl3) δ 1258 1262 1291 1370 1407 IR (KBr) 3068 2923 2360 1647 1381 694 cmminus1 Anal Calcd for C30H18S6 C 6312 H 318 Found C 6308 H 336 In a similar manner the Rhamine-catalyzed cyclotrimerization of di(thienyl)acetylene derivatives 1indash1k was carried out The reaction conditions and the results are illustrated in Table 5 Hexakis(5-methyl-2-thienyl)benzene (2i) Yellow solids Rf = 023 (hexanetoluene 51) 1H NMR (600 MHz CDCl3) δ 633 (s 12H) 230 (s 18H) 13C NMR (150 MHz CDCl3) δ 152 1239 1287 1370 1388 1402 IR (KBr) 3068 2912 2855 2357 1747 1442 1219 800 cmminus1 Anal Calcd for C36H30S6 C 6601 H 462 Found C 6609 H 453 Hexakis(5-acetyl-2-thienyl)benzene (2j) Colorless solids Rf = 007 (hexaneEtOAc 31) 1H NMR (600 MHz CDCl3) δ 727 (d J = 36 Hz 6H) 667 (d J = 36 Hz 6H) 243 (s 18H) 13C NMR (150 MHz CDCl3) δ 267 1309 1318 1365 1458 1467 1907 IR (KBr) 3080 1658 1471 1381 1274 cmminus1
434 Hexa(3-thienyl)benzene (2k) Brown solids Rf = 027 (hexaneEtOAc 31) 1H NMR (600 MHz CDCl3) δ 691 (dd J = 48 30 Hz 6H) 658 (dd J = 30 15 Hz 6H) 650 (dd J = 48 36 Hz 6H) 13C NMR (150 MHz CDCl3) δ 1233 1241 1297 1365 1403 IR (KBr) 3068 2923 2360 1647 1381 1223 694 cmminus1 Anal Calcd for C30H18S6 C 6312 H 318 Found C 6308 H 336 General procedure for Rhamine-catalyzed cyclotrimerization of terminal alkyne To a suspension of RhCl3bull3H2O (11 mg 004 mmol) in toluene (30 mL) were added i-Pr2NEt (26 μL 015 mmol) and phenylacetylene 1l (55 mg 050 mmol) The mixture was stirred at reflux for 12 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford 124-triphenylbenzene 2l (54 mg 98) as colorless solids 124-Triphenylbenzene (2l)67
Colorless solids Rf = 057 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 717ndash724 (m 10H) 737 (tt J = 78 12 Hz 1H) 745ndash748 (m 2H) 751 (dd J = 78 12 Hz 1H) 765ndash769 (m 4H) 13C NMR (150 MHz CDCl3) δ 1261 1265 1266 1271 1274 12789 12792 1288 1294 12987 12990 1311 1395 1404 1406 1410 1411 1415 IR (KBr) 3075 3056 3027 cmndash1 In a similar manner the Rhamine-catalyzed cyclotrimerization of terminal alkynes 1mndash1o was conducted The reaction conditions and the results are illustrated in Table 5 124-Tris(4-methylphenyl)benzene (2m)58 Colorless solids Rf = 060 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 232 (s 3H) 233 (s 3H) 240 (s 3H) 703ndash710 (m 8H) 726 (dd J = 78 06 Hz 2H) 746 (dd J = 78 06 Hz 1H) 756ndash762 (m 4H) 13C NMR (150 MHz CDCl3) δ 2111 2113 1257 1269 1286 1287 1292 1295 12968 12971 1311 1360 1361 1371 1378 1383 1387 1391 1400 1408 IR (KBr) 3025 2917 2863 cmndash1 Anal Calcd for C27H24 C 9306 H 694 Found C 9267 H 733 124-Trihexylbenzene (2n)5
Colorless liquid Rf = 077 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 087ndash091 (m 9H) 128ndash139 (m 18H) 154ndash159 (m 6H) 252ndash258 (m 6H) 692 (dd J = 78 18 Hz 1H) 695 (d J = 18 Hz 1H) 704 (d J = 78 Hz 1H) 124-Triethoxycarbonylbenzene (2o)9 Yellow liquid Rf = 023 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 138 (t J = 72 Hz 3H) 139 (t J = 72 Hz 3H) 141 (t J = 72 Hz 3H) 439 (q J = 72 Hz 4H) 441 (q J = 72 Hz 2H)
776 (dd J = 84 06 Hz 1H) 819 (dd J = 84 12 Hz 1H) 840 (dd J = 12 06 Hz 1H) 13C NMR (150 MHz CDCl3) δ 140 141 142 617 619 620 1288 1301 13200 13204 1327 1362 1650 1666 1672 IR (neat) 2983 2938 1727 1244 cmndash1 Anal Calcd for C15H18O6 C 6122 H 616 Found C 6114 H 660 135-Triethoxycarbonylbenzene (3o)10
Colorless solids Rf = 023 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 143 (t J = 72 Hz 9H) 444 (q J = 72 Hz 6H) 885 (s 3H) 13C NMR (150 MHz CDCl3) δ 143 617 1314 1344 1651 IR (KBr) 2943 2907 2877 1724 1240 cmndash1 Anal Calcd for C15H18O6 C 6122 H 616 Found C 6146 H 628 Synthesis of RhCl3bull3H2Oi-Pr2NEt complex To a solution of RhCl3bull3H2O (26 mg 01 mmol) in i-PrOH (6 mL) was added i-Pr2NEt (51 μL 03 mmol) The mixture was stirred at room temperature (or reflux) for 05 h and was oncentrated under reduced pressure The residue was purified by gel permeation chromatography Then the solid was purified by recyclization and colorless crystals were obtained General Procedure for Cyclization of Diyne 4a and Alkyne 1 To a solution of RhCl3bull3H2O (11 mg 004 mmol) and i-Pr2NEt (26 μL 015 mmol) in i-PrOH (20 mL) were added phenylacetylene 1l (217 mg 20 mmol) and diyne 4a (116 mg 049 mmol) in i-PrOH (30 mL) The mixture was stirred at reflux for 2 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford diethyl 5-phenyl-1H-indene-22(3H)-dicarboxylate 5al (138 mg 81) as yellow liquid Diethyl 5-Phenyl-1H-indene-22(3H)-dicarboxylate (5al)11
Yellow liquid Rf = 037 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 125ndash128 (m 6H) 363 (s 2H) 366 (s 2H) 426 (q J = 72 Hz 4H) 726ndash727 (m 1H) 732ndash734 (m 1H) 739ndash743 (m 4H) 755ndash756 (m 2H) 13C NMR (150 MHz CDCl3) δ 140 402 404 605 617 1230 1244 1261 1270 1271 1286 1391 1403 1407 1413 1716 IR (neat) 3031 2980 2936 1733 cmndash1 Anal Calcd for C21H22O4 C 7454 H 656 Found C 7453 H 674 In a similar manner the Rhamine-catalyzed cyclotrimerization of diyne 4a and alkynes 1a 1c 1f and 1n was carried out The reaction conditions and the results are illustrated in Table 6 Diethyl 5-Hexyl-1H-indene-22(3H)-dicarboxylate (5an)4
Orange liquid Rf = 047 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 087ndash089 (m 3H)
124ndash133 (m 12H) 154ndash160 (m 2H) 254 (t J = 72 Hz 2H) 355 (s 2H) 356 (s 2H) 420 (q J = 72 Hz 4H) 697 (d J = 72 Hz 1H) 701 (s 1H) 708 (d J = 72 Hz 1H) 13C NMR (150 MHz CDCl3) δ 140 141 226 290 3169 3172 358 401 404 605 616 1238 1241 1271 1371 1400 1418 1718 IR (neat) 2957 2928 2856 1735 cmndash1 Anal Calcd for C21H30O4 C 7280 H 873 Found C 7279 H 884 Diethyl 5-Ethoxycarbonyl 6-Phenyl-1H-indene-22(3H)-dicarboxylate (5aa) Colorless solids Rf = 026 (hexaneEtOAc 41) 1H NMR (600 MHz CDCl3) δ 096 (t J = 72 Hz 3H) 127 (t J = 72 Hz 6H) 363 (s 2H) 365 (s 2H) 404 (q J = 72 Hz 2H) 422 (q J = 72 Hz 2H) 719 (d J = 06 Hz 1H) 726ndash728 (m 2H) 730ndash737 (m 2H) 766 (s 1H) 13C NMR (150 MHz CDCl3) δ 136 140 400 404 604 608 618 1255 1264 1269 1279 1283 1302 1392 14166 14174 1437 1688 1713 IR (KBr) 3059 3024 2980 2935 2905 1732 cmndash1 Anal Calcd for C24H26O6 C 7023 H 638 Found C 7015 H 644 Diethyl 5-Methyl 6-Phenyl-1H-indene-22(3H)-dicarboxylate (5ac) Yellow liquid Rf = 040 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 127 (t J = 72 Hz 6H) 221 (s 3H) 359 (s 2H) 360 (s 2H) 422 (q J = 72 Hz 4H) 705 (s 1H) 710 (s 1H) 728ndash733 (m 3H) 737ndash740 (m 2H) 13C NMR (150 MHz CDCl3) δ 140 204 402 403 605 617 1255 1266 1280 1292 1341 1375 1391 1408 1421 1717 IR (neat) 3057 2980 2935 1733 1244 cmndash1 Anal Calcd for C22H24O4 C 7498 H 686 Found C 7493 H 699 Diethyl 56-Diphenyl-1H-indene-22(3H)-dicarboxylate (5af) Colorless solids Rf = 039 (hexaneEtOAc 41) 1H NMR (600 MHz CDCl3) δ 1281 (t J = 72 Hz 3H) 1282 (t J = 72 Hz 3H) 368 (s 4H) 4240 (q J = 72 Hz 2H) 4241 (q J = 72 Hz 2H) 709ndash711 (m 4H) 715ndash720 (m 6H) 725 (d J = 06 Hz 2H) 13C NMR (150 MHz CDCl3) δ 140 403 605 618 1263 1278 1299 1394 1396 1416 1717 IR (KBr) 3057 2985 2903 1732 1708 cmndash1 General Procedure for Cyclization of Diyne 4b and Alkyne 1f To a solution of RhCl3bull3H2O (11 mg 004 mmol) and i-Pr2NEt (26 μL 015 mmol) in i-PrOH (20 mL) were added diphenylacetylene 1f (900 mg 50 mmol) and diyne 4b (132 mg 050 mmol) in i-PrOH (30 mL) The mixture was stirred at reflux for 24 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford 47-dimethyl-56-diphenyl-indan-22-dicarboxylic acid diethyl ester 5bf (102 mg 46) and 45 of 4b was recovered
Diethyl 47-Dimethyl-56-diphenyl-1H-indene-22(3H)-dicarboxylate (5bf) Red liquid Rf = 050 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 132 (t J = 72 Hz 6H) 200 (s 6H) 369 (s 4H) 428 (q J = 72 Hz 4H) 692 (d J = 72 Hz 4H) 704ndash706 (m 2H) 710ndash712 (m 4H) 13C NMR (150 MHz CDCl3) δ 137 192 307 644 1182 1280 1288 1302 1344 1445 1671 IR (neat) 3056 3021 2981 2935 1733 1242 cmndash1 Reference 1 Bhar S Chaudhuri K S Sahu S G Panja C Tetrahedron 2001 57 9011ndash9016 2 Diercks R tom Dieck H Z Naturforsch B Chem Sc 1984 39B 180ndash184 3 Sigman M S Fatland A W Eaton B E J Am Chem Soc 1998 120 5130ndash5131 4 Mori N Ikeda S Odashima K Chem Commun 2001 181ndash182 5 Li J Jiang H Chen M J Org Chem 2001 66 3627ndash3629 6 Rodriacuteguez J G Lafuente A Martiacuten-Villamil R J Polym Sci Part A Polym Chem 2005 43 1228ndash1237 7 Yasuda M Kojima R Tsutsui H Utsunomiya D Ishii K Jinnouchi K Shiragami T J Org Chem 2003 68 7618ndash7624 8 Tagliatesta P Floris B Galloni P Leoni A DrsquoArcangelo G Inorg Chem 2003 42 7701ndash7703 9 Tanaka K Toyoda K Wada A Shirasaki K Hirano M Chem Eur J 2005 11 1145ndash1156 10 Kanner C B Pandit U K Tetrahedron 1982 38 3597ndash3604 11 Hilt G Vogler T Hess W Galbiati F Chem Commun 2005 1474ndash1475
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CO2MeCO2MeMeO2C
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CO2MeCO2MeMeO2C
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2g
2h
S
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SS
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2h
S
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S
2i
S
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S
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S
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Ph
Ph
2l
PhH
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5an
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Hexaphenylbenzene (2f)3
Colorless solids Rf = 050 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 683ndash686 (m 30H) 13C NMR (150 MHz CDCl3) δ 1252 1265 1314 1403 1406 IR (KBr) 3056 3024 2925 cmndash1 Hexamethoxycarbonylbenzene (2g)
Colorless solids Rf = 031 (hexaneEtOAc 11) 1H NMR (600 MHz CDCl3) δ 388 (s 18H) 13C NMR (150 MHz CDCl3) δ 535 1339 1651 IR (KBr) 3009 2958 1739 1445 cmminus1 Anal Calcd for C18H18O6 C 5071 H 426 Found C 5077 H 399 General procedure for Rhamine-catalyzed cyclotrimerization of di(thienyl)acetylene To a solution of RhCl33H2O (11 mg 004 mmol) in i-PrOH (30 mL) were added i-Pr2NEt (26 μL 015 mmol) and di(2-thienyl)acetylene 1h (96 mg 050 mmol) The mixture was stirred at reflux for 24 h After being cooled to room temperature the reaction mixture was filtered and concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexanetoluene 51) to afford hexa(2-thienyl)benzene 2h (47 mg 49) as yellow solids Hexa(2-thienyl)benzene (2h) Yellow solids Rf = 027 (hexanetoluene 51) 1H NMR (600 MHz CDCl3) δ 659 (dd J = 36 12 Hz 6H) 668 (dd J = 54 36 Hz 6H) 708 (dd J = 54 12 Hz 6H) 13C NMR (150 MHz CDCl3) δ 1258 1262 1291 1370 1407 IR (KBr) 3068 2923 2360 1647 1381 694 cmminus1 Anal Calcd for C30H18S6 C 6312 H 318 Found C 6308 H 336 In a similar manner the Rhamine-catalyzed cyclotrimerization of di(thienyl)acetylene derivatives 1indash1k was carried out The reaction conditions and the results are illustrated in Table 5 Hexakis(5-methyl-2-thienyl)benzene (2i) Yellow solids Rf = 023 (hexanetoluene 51) 1H NMR (600 MHz CDCl3) δ 633 (s 12H) 230 (s 18H) 13C NMR (150 MHz CDCl3) δ 152 1239 1287 1370 1388 1402 IR (KBr) 3068 2912 2855 2357 1747 1442 1219 800 cmminus1 Anal Calcd for C36H30S6 C 6601 H 462 Found C 6609 H 453 Hexakis(5-acetyl-2-thienyl)benzene (2j) Colorless solids Rf = 007 (hexaneEtOAc 31) 1H NMR (600 MHz CDCl3) δ 727 (d J = 36 Hz 6H) 667 (d J = 36 Hz 6H) 243 (s 18H) 13C NMR (150 MHz CDCl3) δ 267 1309 1318 1365 1458 1467 1907 IR (KBr) 3080 1658 1471 1381 1274 cmminus1
434 Hexa(3-thienyl)benzene (2k) Brown solids Rf = 027 (hexaneEtOAc 31) 1H NMR (600 MHz CDCl3) δ 691 (dd J = 48 30 Hz 6H) 658 (dd J = 30 15 Hz 6H) 650 (dd J = 48 36 Hz 6H) 13C NMR (150 MHz CDCl3) δ 1233 1241 1297 1365 1403 IR (KBr) 3068 2923 2360 1647 1381 1223 694 cmminus1 Anal Calcd for C30H18S6 C 6312 H 318 Found C 6308 H 336 General procedure for Rhamine-catalyzed cyclotrimerization of terminal alkyne To a suspension of RhCl3bull3H2O (11 mg 004 mmol) in toluene (30 mL) were added i-Pr2NEt (26 μL 015 mmol) and phenylacetylene 1l (55 mg 050 mmol) The mixture was stirred at reflux for 12 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford 124-triphenylbenzene 2l (54 mg 98) as colorless solids 124-Triphenylbenzene (2l)67
Colorless solids Rf = 057 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 717ndash724 (m 10H) 737 (tt J = 78 12 Hz 1H) 745ndash748 (m 2H) 751 (dd J = 78 12 Hz 1H) 765ndash769 (m 4H) 13C NMR (150 MHz CDCl3) δ 1261 1265 1266 1271 1274 12789 12792 1288 1294 12987 12990 1311 1395 1404 1406 1410 1411 1415 IR (KBr) 3075 3056 3027 cmndash1 In a similar manner the Rhamine-catalyzed cyclotrimerization of terminal alkynes 1mndash1o was conducted The reaction conditions and the results are illustrated in Table 5 124-Tris(4-methylphenyl)benzene (2m)58 Colorless solids Rf = 060 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 232 (s 3H) 233 (s 3H) 240 (s 3H) 703ndash710 (m 8H) 726 (dd J = 78 06 Hz 2H) 746 (dd J = 78 06 Hz 1H) 756ndash762 (m 4H) 13C NMR (150 MHz CDCl3) δ 2111 2113 1257 1269 1286 1287 1292 1295 12968 12971 1311 1360 1361 1371 1378 1383 1387 1391 1400 1408 IR (KBr) 3025 2917 2863 cmndash1 Anal Calcd for C27H24 C 9306 H 694 Found C 9267 H 733 124-Trihexylbenzene (2n)5
Colorless liquid Rf = 077 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 087ndash091 (m 9H) 128ndash139 (m 18H) 154ndash159 (m 6H) 252ndash258 (m 6H) 692 (dd J = 78 18 Hz 1H) 695 (d J = 18 Hz 1H) 704 (d J = 78 Hz 1H) 124-Triethoxycarbonylbenzene (2o)9 Yellow liquid Rf = 023 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 138 (t J = 72 Hz 3H) 139 (t J = 72 Hz 3H) 141 (t J = 72 Hz 3H) 439 (q J = 72 Hz 4H) 441 (q J = 72 Hz 2H)
776 (dd J = 84 06 Hz 1H) 819 (dd J = 84 12 Hz 1H) 840 (dd J = 12 06 Hz 1H) 13C NMR (150 MHz CDCl3) δ 140 141 142 617 619 620 1288 1301 13200 13204 1327 1362 1650 1666 1672 IR (neat) 2983 2938 1727 1244 cmndash1 Anal Calcd for C15H18O6 C 6122 H 616 Found C 6114 H 660 135-Triethoxycarbonylbenzene (3o)10
Colorless solids Rf = 023 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 143 (t J = 72 Hz 9H) 444 (q J = 72 Hz 6H) 885 (s 3H) 13C NMR (150 MHz CDCl3) δ 143 617 1314 1344 1651 IR (KBr) 2943 2907 2877 1724 1240 cmndash1 Anal Calcd for C15H18O6 C 6122 H 616 Found C 6146 H 628 Synthesis of RhCl3bull3H2Oi-Pr2NEt complex To a solution of RhCl3bull3H2O (26 mg 01 mmol) in i-PrOH (6 mL) was added i-Pr2NEt (51 μL 03 mmol) The mixture was stirred at room temperature (or reflux) for 05 h and was oncentrated under reduced pressure The residue was purified by gel permeation chromatography Then the solid was purified by recyclization and colorless crystals were obtained General Procedure for Cyclization of Diyne 4a and Alkyne 1 To a solution of RhCl3bull3H2O (11 mg 004 mmol) and i-Pr2NEt (26 μL 015 mmol) in i-PrOH (20 mL) were added phenylacetylene 1l (217 mg 20 mmol) and diyne 4a (116 mg 049 mmol) in i-PrOH (30 mL) The mixture was stirred at reflux for 2 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford diethyl 5-phenyl-1H-indene-22(3H)-dicarboxylate 5al (138 mg 81) as yellow liquid Diethyl 5-Phenyl-1H-indene-22(3H)-dicarboxylate (5al)11
Yellow liquid Rf = 037 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 125ndash128 (m 6H) 363 (s 2H) 366 (s 2H) 426 (q J = 72 Hz 4H) 726ndash727 (m 1H) 732ndash734 (m 1H) 739ndash743 (m 4H) 755ndash756 (m 2H) 13C NMR (150 MHz CDCl3) δ 140 402 404 605 617 1230 1244 1261 1270 1271 1286 1391 1403 1407 1413 1716 IR (neat) 3031 2980 2936 1733 cmndash1 Anal Calcd for C21H22O4 C 7454 H 656 Found C 7453 H 674 In a similar manner the Rhamine-catalyzed cyclotrimerization of diyne 4a and alkynes 1a 1c 1f and 1n was carried out The reaction conditions and the results are illustrated in Table 6 Diethyl 5-Hexyl-1H-indene-22(3H)-dicarboxylate (5an)4
Orange liquid Rf = 047 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 087ndash089 (m 3H)
124ndash133 (m 12H) 154ndash160 (m 2H) 254 (t J = 72 Hz 2H) 355 (s 2H) 356 (s 2H) 420 (q J = 72 Hz 4H) 697 (d J = 72 Hz 1H) 701 (s 1H) 708 (d J = 72 Hz 1H) 13C NMR (150 MHz CDCl3) δ 140 141 226 290 3169 3172 358 401 404 605 616 1238 1241 1271 1371 1400 1418 1718 IR (neat) 2957 2928 2856 1735 cmndash1 Anal Calcd for C21H30O4 C 7280 H 873 Found C 7279 H 884 Diethyl 5-Ethoxycarbonyl 6-Phenyl-1H-indene-22(3H)-dicarboxylate (5aa) Colorless solids Rf = 026 (hexaneEtOAc 41) 1H NMR (600 MHz CDCl3) δ 096 (t J = 72 Hz 3H) 127 (t J = 72 Hz 6H) 363 (s 2H) 365 (s 2H) 404 (q J = 72 Hz 2H) 422 (q J = 72 Hz 2H) 719 (d J = 06 Hz 1H) 726ndash728 (m 2H) 730ndash737 (m 2H) 766 (s 1H) 13C NMR (150 MHz CDCl3) δ 136 140 400 404 604 608 618 1255 1264 1269 1279 1283 1302 1392 14166 14174 1437 1688 1713 IR (KBr) 3059 3024 2980 2935 2905 1732 cmndash1 Anal Calcd for C24H26O6 C 7023 H 638 Found C 7015 H 644 Diethyl 5-Methyl 6-Phenyl-1H-indene-22(3H)-dicarboxylate (5ac) Yellow liquid Rf = 040 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 127 (t J = 72 Hz 6H) 221 (s 3H) 359 (s 2H) 360 (s 2H) 422 (q J = 72 Hz 4H) 705 (s 1H) 710 (s 1H) 728ndash733 (m 3H) 737ndash740 (m 2H) 13C NMR (150 MHz CDCl3) δ 140 204 402 403 605 617 1255 1266 1280 1292 1341 1375 1391 1408 1421 1717 IR (neat) 3057 2980 2935 1733 1244 cmndash1 Anal Calcd for C22H24O4 C 7498 H 686 Found C 7493 H 699 Diethyl 56-Diphenyl-1H-indene-22(3H)-dicarboxylate (5af) Colorless solids Rf = 039 (hexaneEtOAc 41) 1H NMR (600 MHz CDCl3) δ 1281 (t J = 72 Hz 3H) 1282 (t J = 72 Hz 3H) 368 (s 4H) 4240 (q J = 72 Hz 2H) 4241 (q J = 72 Hz 2H) 709ndash711 (m 4H) 715ndash720 (m 6H) 725 (d J = 06 Hz 2H) 13C NMR (150 MHz CDCl3) δ 140 403 605 618 1263 1278 1299 1394 1396 1416 1717 IR (KBr) 3057 2985 2903 1732 1708 cmndash1 General Procedure for Cyclization of Diyne 4b and Alkyne 1f To a solution of RhCl3bull3H2O (11 mg 004 mmol) and i-Pr2NEt (26 μL 015 mmol) in i-PrOH (20 mL) were added diphenylacetylene 1f (900 mg 50 mmol) and diyne 4b (132 mg 050 mmol) in i-PrOH (30 mL) The mixture was stirred at reflux for 24 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford 47-dimethyl-56-diphenyl-indan-22-dicarboxylic acid diethyl ester 5bf (102 mg 46) and 45 of 4b was recovered
Diethyl 47-Dimethyl-56-diphenyl-1H-indene-22(3H)-dicarboxylate (5bf) Red liquid Rf = 050 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 132 (t J = 72 Hz 6H) 200 (s 6H) 369 (s 4H) 428 (q J = 72 Hz 4H) 692 (d J = 72 Hz 4H) 704ndash706 (m 2H) 710ndash712 (m 4H) 13C NMR (150 MHz CDCl3) δ 137 192 307 644 1182 1280 1288 1302 1344 1445 1671 IR (neat) 3056 3021 2981 2935 1733 1242 cmndash1 Reference 1 Bhar S Chaudhuri K S Sahu S G Panja C Tetrahedron 2001 57 9011ndash9016 2 Diercks R tom Dieck H Z Naturforsch B Chem Sc 1984 39B 180ndash184 3 Sigman M S Fatland A W Eaton B E J Am Chem Soc 1998 120 5130ndash5131 4 Mori N Ikeda S Odashima K Chem Commun 2001 181ndash182 5 Li J Jiang H Chen M J Org Chem 2001 66 3627ndash3629 6 Rodriacuteguez J G Lafuente A Martiacuten-Villamil R J Polym Sci Part A Polym Chem 2005 43 1228ndash1237 7 Yasuda M Kojima R Tsutsui H Utsunomiya D Ishii K Jinnouchi K Shiragami T J Org Chem 2003 68 7618ndash7624 8 Tagliatesta P Floris B Galloni P Leoni A DrsquoArcangelo G Inorg Chem 2003 42 7701ndash7703 9 Tanaka K Toyoda K Wada A Shirasaki K Hirano M Chem Eur J 2005 11 1145ndash1156 10 Kanner C B Pandit U K Tetrahedron 1982 38 3597ndash3604 11 Hilt G Vogler T Hess W Galbiati F Chem Commun 2005 1474ndash1475
PhPh
PhCO2EtEtO2C
EtO2C
2a
PhPh
PhCO2EtEtO2C
EtO2C
2a
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhMeMe
Me
2c
PhPh
PhMeMe
Me
2c
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeCO2Et
CO2EtMeMe
EtO2C
3d
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
434 Hexa(3-thienyl)benzene (2k) Brown solids Rf = 027 (hexaneEtOAc 31) 1H NMR (600 MHz CDCl3) δ 691 (dd J = 48 30 Hz 6H) 658 (dd J = 30 15 Hz 6H) 650 (dd J = 48 36 Hz 6H) 13C NMR (150 MHz CDCl3) δ 1233 1241 1297 1365 1403 IR (KBr) 3068 2923 2360 1647 1381 1223 694 cmminus1 Anal Calcd for C30H18S6 C 6312 H 318 Found C 6308 H 336 General procedure for Rhamine-catalyzed cyclotrimerization of terminal alkyne To a suspension of RhCl3bull3H2O (11 mg 004 mmol) in toluene (30 mL) were added i-Pr2NEt (26 μL 015 mmol) and phenylacetylene 1l (55 mg 050 mmol) The mixture was stirred at reflux for 12 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford 124-triphenylbenzene 2l (54 mg 98) as colorless solids 124-Triphenylbenzene (2l)67
Colorless solids Rf = 057 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 717ndash724 (m 10H) 737 (tt J = 78 12 Hz 1H) 745ndash748 (m 2H) 751 (dd J = 78 12 Hz 1H) 765ndash769 (m 4H) 13C NMR (150 MHz CDCl3) δ 1261 1265 1266 1271 1274 12789 12792 1288 1294 12987 12990 1311 1395 1404 1406 1410 1411 1415 IR (KBr) 3075 3056 3027 cmndash1 In a similar manner the Rhamine-catalyzed cyclotrimerization of terminal alkynes 1mndash1o was conducted The reaction conditions and the results are illustrated in Table 5 124-Tris(4-methylphenyl)benzene (2m)58 Colorless solids Rf = 060 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 232 (s 3H) 233 (s 3H) 240 (s 3H) 703ndash710 (m 8H) 726 (dd J = 78 06 Hz 2H) 746 (dd J = 78 06 Hz 1H) 756ndash762 (m 4H) 13C NMR (150 MHz CDCl3) δ 2111 2113 1257 1269 1286 1287 1292 1295 12968 12971 1311 1360 1361 1371 1378 1383 1387 1391 1400 1408 IR (KBr) 3025 2917 2863 cmndash1 Anal Calcd for C27H24 C 9306 H 694 Found C 9267 H 733 124-Trihexylbenzene (2n)5
Colorless liquid Rf = 077 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 087ndash091 (m 9H) 128ndash139 (m 18H) 154ndash159 (m 6H) 252ndash258 (m 6H) 692 (dd J = 78 18 Hz 1H) 695 (d J = 18 Hz 1H) 704 (d J = 78 Hz 1H) 124-Triethoxycarbonylbenzene (2o)9 Yellow liquid Rf = 023 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 138 (t J = 72 Hz 3H) 139 (t J = 72 Hz 3H) 141 (t J = 72 Hz 3H) 439 (q J = 72 Hz 4H) 441 (q J = 72 Hz 2H)
776 (dd J = 84 06 Hz 1H) 819 (dd J = 84 12 Hz 1H) 840 (dd J = 12 06 Hz 1H) 13C NMR (150 MHz CDCl3) δ 140 141 142 617 619 620 1288 1301 13200 13204 1327 1362 1650 1666 1672 IR (neat) 2983 2938 1727 1244 cmndash1 Anal Calcd for C15H18O6 C 6122 H 616 Found C 6114 H 660 135-Triethoxycarbonylbenzene (3o)10
Colorless solids Rf = 023 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 143 (t J = 72 Hz 9H) 444 (q J = 72 Hz 6H) 885 (s 3H) 13C NMR (150 MHz CDCl3) δ 143 617 1314 1344 1651 IR (KBr) 2943 2907 2877 1724 1240 cmndash1 Anal Calcd for C15H18O6 C 6122 H 616 Found C 6146 H 628 Synthesis of RhCl3bull3H2Oi-Pr2NEt complex To a solution of RhCl3bull3H2O (26 mg 01 mmol) in i-PrOH (6 mL) was added i-Pr2NEt (51 μL 03 mmol) The mixture was stirred at room temperature (or reflux) for 05 h and was oncentrated under reduced pressure The residue was purified by gel permeation chromatography Then the solid was purified by recyclization and colorless crystals were obtained General Procedure for Cyclization of Diyne 4a and Alkyne 1 To a solution of RhCl3bull3H2O (11 mg 004 mmol) and i-Pr2NEt (26 μL 015 mmol) in i-PrOH (20 mL) were added phenylacetylene 1l (217 mg 20 mmol) and diyne 4a (116 mg 049 mmol) in i-PrOH (30 mL) The mixture was stirred at reflux for 2 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford diethyl 5-phenyl-1H-indene-22(3H)-dicarboxylate 5al (138 mg 81) as yellow liquid Diethyl 5-Phenyl-1H-indene-22(3H)-dicarboxylate (5al)11
Yellow liquid Rf = 037 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 125ndash128 (m 6H) 363 (s 2H) 366 (s 2H) 426 (q J = 72 Hz 4H) 726ndash727 (m 1H) 732ndash734 (m 1H) 739ndash743 (m 4H) 755ndash756 (m 2H) 13C NMR (150 MHz CDCl3) δ 140 402 404 605 617 1230 1244 1261 1270 1271 1286 1391 1403 1407 1413 1716 IR (neat) 3031 2980 2936 1733 cmndash1 Anal Calcd for C21H22O4 C 7454 H 656 Found C 7453 H 674 In a similar manner the Rhamine-catalyzed cyclotrimerization of diyne 4a and alkynes 1a 1c 1f and 1n was carried out The reaction conditions and the results are illustrated in Table 6 Diethyl 5-Hexyl-1H-indene-22(3H)-dicarboxylate (5an)4
Orange liquid Rf = 047 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 087ndash089 (m 3H)
124ndash133 (m 12H) 154ndash160 (m 2H) 254 (t J = 72 Hz 2H) 355 (s 2H) 356 (s 2H) 420 (q J = 72 Hz 4H) 697 (d J = 72 Hz 1H) 701 (s 1H) 708 (d J = 72 Hz 1H) 13C NMR (150 MHz CDCl3) δ 140 141 226 290 3169 3172 358 401 404 605 616 1238 1241 1271 1371 1400 1418 1718 IR (neat) 2957 2928 2856 1735 cmndash1 Anal Calcd for C21H30O4 C 7280 H 873 Found C 7279 H 884 Diethyl 5-Ethoxycarbonyl 6-Phenyl-1H-indene-22(3H)-dicarboxylate (5aa) Colorless solids Rf = 026 (hexaneEtOAc 41) 1H NMR (600 MHz CDCl3) δ 096 (t J = 72 Hz 3H) 127 (t J = 72 Hz 6H) 363 (s 2H) 365 (s 2H) 404 (q J = 72 Hz 2H) 422 (q J = 72 Hz 2H) 719 (d J = 06 Hz 1H) 726ndash728 (m 2H) 730ndash737 (m 2H) 766 (s 1H) 13C NMR (150 MHz CDCl3) δ 136 140 400 404 604 608 618 1255 1264 1269 1279 1283 1302 1392 14166 14174 1437 1688 1713 IR (KBr) 3059 3024 2980 2935 2905 1732 cmndash1 Anal Calcd for C24H26O6 C 7023 H 638 Found C 7015 H 644 Diethyl 5-Methyl 6-Phenyl-1H-indene-22(3H)-dicarboxylate (5ac) Yellow liquid Rf = 040 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 127 (t J = 72 Hz 6H) 221 (s 3H) 359 (s 2H) 360 (s 2H) 422 (q J = 72 Hz 4H) 705 (s 1H) 710 (s 1H) 728ndash733 (m 3H) 737ndash740 (m 2H) 13C NMR (150 MHz CDCl3) δ 140 204 402 403 605 617 1255 1266 1280 1292 1341 1375 1391 1408 1421 1717 IR (neat) 3057 2980 2935 1733 1244 cmndash1 Anal Calcd for C22H24O4 C 7498 H 686 Found C 7493 H 699 Diethyl 56-Diphenyl-1H-indene-22(3H)-dicarboxylate (5af) Colorless solids Rf = 039 (hexaneEtOAc 41) 1H NMR (600 MHz CDCl3) δ 1281 (t J = 72 Hz 3H) 1282 (t J = 72 Hz 3H) 368 (s 4H) 4240 (q J = 72 Hz 2H) 4241 (q J = 72 Hz 2H) 709ndash711 (m 4H) 715ndash720 (m 6H) 725 (d J = 06 Hz 2H) 13C NMR (150 MHz CDCl3) δ 140 403 605 618 1263 1278 1299 1394 1396 1416 1717 IR (KBr) 3057 2985 2903 1732 1708 cmndash1 General Procedure for Cyclization of Diyne 4b and Alkyne 1f To a solution of RhCl3bull3H2O (11 mg 004 mmol) and i-Pr2NEt (26 μL 015 mmol) in i-PrOH (20 mL) were added diphenylacetylene 1f (900 mg 50 mmol) and diyne 4b (132 mg 050 mmol) in i-PrOH (30 mL) The mixture was stirred at reflux for 24 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford 47-dimethyl-56-diphenyl-indan-22-dicarboxylic acid diethyl ester 5bf (102 mg 46) and 45 of 4b was recovered
Diethyl 47-Dimethyl-56-diphenyl-1H-indene-22(3H)-dicarboxylate (5bf) Red liquid Rf = 050 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 132 (t J = 72 Hz 6H) 200 (s 6H) 369 (s 4H) 428 (q J = 72 Hz 4H) 692 (d J = 72 Hz 4H) 704ndash706 (m 2H) 710ndash712 (m 4H) 13C NMR (150 MHz CDCl3) δ 137 192 307 644 1182 1280 1288 1302 1344 1445 1671 IR (neat) 3056 3021 2981 2935 1733 1242 cmndash1 Reference 1 Bhar S Chaudhuri K S Sahu S G Panja C Tetrahedron 2001 57 9011ndash9016 2 Diercks R tom Dieck H Z Naturforsch B Chem Sc 1984 39B 180ndash184 3 Sigman M S Fatland A W Eaton B E J Am Chem Soc 1998 120 5130ndash5131 4 Mori N Ikeda S Odashima K Chem Commun 2001 181ndash182 5 Li J Jiang H Chen M J Org Chem 2001 66 3627ndash3629 6 Rodriacuteguez J G Lafuente A Martiacuten-Villamil R J Polym Sci Part A Polym Chem 2005 43 1228ndash1237 7 Yasuda M Kojima R Tsutsui H Utsunomiya D Ishii K Jinnouchi K Shiragami T J Org Chem 2003 68 7618ndash7624 8 Tagliatesta P Floris B Galloni P Leoni A DrsquoArcangelo G Inorg Chem 2003 42 7701ndash7703 9 Tanaka K Toyoda K Wada A Shirasaki K Hirano M Chem Eur J 2005 11 1145ndash1156 10 Kanner C B Pandit U K Tetrahedron 1982 38 3597ndash3604 11 Hilt G Vogler T Hess W Galbiati F Chem Commun 2005 1474ndash1475
PhPh
PhCO2EtEtO2C
EtO2C
2a
PhPh
PhCO2EtEtO2C
EtO2C
2a
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhMeMe
Me
2c
PhPh
PhMeMe
Me
2c
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeCO2Et
CO2EtMeMe
EtO2C
3d
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
776 (dd J = 84 06 Hz 1H) 819 (dd J = 84 12 Hz 1H) 840 (dd J = 12 06 Hz 1H) 13C NMR (150 MHz CDCl3) δ 140 141 142 617 619 620 1288 1301 13200 13204 1327 1362 1650 1666 1672 IR (neat) 2983 2938 1727 1244 cmndash1 Anal Calcd for C15H18O6 C 6122 H 616 Found C 6114 H 660 135-Triethoxycarbonylbenzene (3o)10
Colorless solids Rf = 023 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 143 (t J = 72 Hz 9H) 444 (q J = 72 Hz 6H) 885 (s 3H) 13C NMR (150 MHz CDCl3) δ 143 617 1314 1344 1651 IR (KBr) 2943 2907 2877 1724 1240 cmndash1 Anal Calcd for C15H18O6 C 6122 H 616 Found C 6146 H 628 Synthesis of RhCl3bull3H2Oi-Pr2NEt complex To a solution of RhCl3bull3H2O (26 mg 01 mmol) in i-PrOH (6 mL) was added i-Pr2NEt (51 μL 03 mmol) The mixture was stirred at room temperature (or reflux) for 05 h and was oncentrated under reduced pressure The residue was purified by gel permeation chromatography Then the solid was purified by recyclization and colorless crystals were obtained General Procedure for Cyclization of Diyne 4a and Alkyne 1 To a solution of RhCl3bull3H2O (11 mg 004 mmol) and i-Pr2NEt (26 μL 015 mmol) in i-PrOH (20 mL) were added phenylacetylene 1l (217 mg 20 mmol) and diyne 4a (116 mg 049 mmol) in i-PrOH (30 mL) The mixture was stirred at reflux for 2 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford diethyl 5-phenyl-1H-indene-22(3H)-dicarboxylate 5al (138 mg 81) as yellow liquid Diethyl 5-Phenyl-1H-indene-22(3H)-dicarboxylate (5al)11
Yellow liquid Rf = 037 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 125ndash128 (m 6H) 363 (s 2H) 366 (s 2H) 426 (q J = 72 Hz 4H) 726ndash727 (m 1H) 732ndash734 (m 1H) 739ndash743 (m 4H) 755ndash756 (m 2H) 13C NMR (150 MHz CDCl3) δ 140 402 404 605 617 1230 1244 1261 1270 1271 1286 1391 1403 1407 1413 1716 IR (neat) 3031 2980 2936 1733 cmndash1 Anal Calcd for C21H22O4 C 7454 H 656 Found C 7453 H 674 In a similar manner the Rhamine-catalyzed cyclotrimerization of diyne 4a and alkynes 1a 1c 1f and 1n was carried out The reaction conditions and the results are illustrated in Table 6 Diethyl 5-Hexyl-1H-indene-22(3H)-dicarboxylate (5an)4
Orange liquid Rf = 047 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 087ndash089 (m 3H)
124ndash133 (m 12H) 154ndash160 (m 2H) 254 (t J = 72 Hz 2H) 355 (s 2H) 356 (s 2H) 420 (q J = 72 Hz 4H) 697 (d J = 72 Hz 1H) 701 (s 1H) 708 (d J = 72 Hz 1H) 13C NMR (150 MHz CDCl3) δ 140 141 226 290 3169 3172 358 401 404 605 616 1238 1241 1271 1371 1400 1418 1718 IR (neat) 2957 2928 2856 1735 cmndash1 Anal Calcd for C21H30O4 C 7280 H 873 Found C 7279 H 884 Diethyl 5-Ethoxycarbonyl 6-Phenyl-1H-indene-22(3H)-dicarboxylate (5aa) Colorless solids Rf = 026 (hexaneEtOAc 41) 1H NMR (600 MHz CDCl3) δ 096 (t J = 72 Hz 3H) 127 (t J = 72 Hz 6H) 363 (s 2H) 365 (s 2H) 404 (q J = 72 Hz 2H) 422 (q J = 72 Hz 2H) 719 (d J = 06 Hz 1H) 726ndash728 (m 2H) 730ndash737 (m 2H) 766 (s 1H) 13C NMR (150 MHz CDCl3) δ 136 140 400 404 604 608 618 1255 1264 1269 1279 1283 1302 1392 14166 14174 1437 1688 1713 IR (KBr) 3059 3024 2980 2935 2905 1732 cmndash1 Anal Calcd for C24H26O6 C 7023 H 638 Found C 7015 H 644 Diethyl 5-Methyl 6-Phenyl-1H-indene-22(3H)-dicarboxylate (5ac) Yellow liquid Rf = 040 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 127 (t J = 72 Hz 6H) 221 (s 3H) 359 (s 2H) 360 (s 2H) 422 (q J = 72 Hz 4H) 705 (s 1H) 710 (s 1H) 728ndash733 (m 3H) 737ndash740 (m 2H) 13C NMR (150 MHz CDCl3) δ 140 204 402 403 605 617 1255 1266 1280 1292 1341 1375 1391 1408 1421 1717 IR (neat) 3057 2980 2935 1733 1244 cmndash1 Anal Calcd for C22H24O4 C 7498 H 686 Found C 7493 H 699 Diethyl 56-Diphenyl-1H-indene-22(3H)-dicarboxylate (5af) Colorless solids Rf = 039 (hexaneEtOAc 41) 1H NMR (600 MHz CDCl3) δ 1281 (t J = 72 Hz 3H) 1282 (t J = 72 Hz 3H) 368 (s 4H) 4240 (q J = 72 Hz 2H) 4241 (q J = 72 Hz 2H) 709ndash711 (m 4H) 715ndash720 (m 6H) 725 (d J = 06 Hz 2H) 13C NMR (150 MHz CDCl3) δ 140 403 605 618 1263 1278 1299 1394 1396 1416 1717 IR (KBr) 3057 2985 2903 1732 1708 cmndash1 General Procedure for Cyclization of Diyne 4b and Alkyne 1f To a solution of RhCl3bull3H2O (11 mg 004 mmol) and i-Pr2NEt (26 μL 015 mmol) in i-PrOH (20 mL) were added diphenylacetylene 1f (900 mg 50 mmol) and diyne 4b (132 mg 050 mmol) in i-PrOH (30 mL) The mixture was stirred at reflux for 24 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford 47-dimethyl-56-diphenyl-indan-22-dicarboxylic acid diethyl ester 5bf (102 mg 46) and 45 of 4b was recovered
Diethyl 47-Dimethyl-56-diphenyl-1H-indene-22(3H)-dicarboxylate (5bf) Red liquid Rf = 050 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 132 (t J = 72 Hz 6H) 200 (s 6H) 369 (s 4H) 428 (q J = 72 Hz 4H) 692 (d J = 72 Hz 4H) 704ndash706 (m 2H) 710ndash712 (m 4H) 13C NMR (150 MHz CDCl3) δ 137 192 307 644 1182 1280 1288 1302 1344 1445 1671 IR (neat) 3056 3021 2981 2935 1733 1242 cmndash1 Reference 1 Bhar S Chaudhuri K S Sahu S G Panja C Tetrahedron 2001 57 9011ndash9016 2 Diercks R tom Dieck H Z Naturforsch B Chem Sc 1984 39B 180ndash184 3 Sigman M S Fatland A W Eaton B E J Am Chem Soc 1998 120 5130ndash5131 4 Mori N Ikeda S Odashima K Chem Commun 2001 181ndash182 5 Li J Jiang H Chen M J Org Chem 2001 66 3627ndash3629 6 Rodriacuteguez J G Lafuente A Martiacuten-Villamil R J Polym Sci Part A Polym Chem 2005 43 1228ndash1237 7 Yasuda M Kojima R Tsutsui H Utsunomiya D Ishii K Jinnouchi K Shiragami T J Org Chem 2003 68 7618ndash7624 8 Tagliatesta P Floris B Galloni P Leoni A DrsquoArcangelo G Inorg Chem 2003 42 7701ndash7703 9 Tanaka K Toyoda K Wada A Shirasaki K Hirano M Chem Eur J 2005 11 1145ndash1156 10 Kanner C B Pandit U K Tetrahedron 1982 38 3597ndash3604 11 Hilt G Vogler T Hess W Galbiati F Chem Commun 2005 1474ndash1475
PhPh
PhCO2EtEtO2C
EtO2C
2a
PhPh
PhCO2EtEtO2C
EtO2C
2a
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhMeMe
Me
2c
PhPh
PhMeMe
Me
2c
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeCO2Et
CO2EtMeMe
EtO2C
3d
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
124ndash133 (m 12H) 154ndash160 (m 2H) 254 (t J = 72 Hz 2H) 355 (s 2H) 356 (s 2H) 420 (q J = 72 Hz 4H) 697 (d J = 72 Hz 1H) 701 (s 1H) 708 (d J = 72 Hz 1H) 13C NMR (150 MHz CDCl3) δ 140 141 226 290 3169 3172 358 401 404 605 616 1238 1241 1271 1371 1400 1418 1718 IR (neat) 2957 2928 2856 1735 cmndash1 Anal Calcd for C21H30O4 C 7280 H 873 Found C 7279 H 884 Diethyl 5-Ethoxycarbonyl 6-Phenyl-1H-indene-22(3H)-dicarboxylate (5aa) Colorless solids Rf = 026 (hexaneEtOAc 41) 1H NMR (600 MHz CDCl3) δ 096 (t J = 72 Hz 3H) 127 (t J = 72 Hz 6H) 363 (s 2H) 365 (s 2H) 404 (q J = 72 Hz 2H) 422 (q J = 72 Hz 2H) 719 (d J = 06 Hz 1H) 726ndash728 (m 2H) 730ndash737 (m 2H) 766 (s 1H) 13C NMR (150 MHz CDCl3) δ 136 140 400 404 604 608 618 1255 1264 1269 1279 1283 1302 1392 14166 14174 1437 1688 1713 IR (KBr) 3059 3024 2980 2935 2905 1732 cmndash1 Anal Calcd for C24H26O6 C 7023 H 638 Found C 7015 H 644 Diethyl 5-Methyl 6-Phenyl-1H-indene-22(3H)-dicarboxylate (5ac) Yellow liquid Rf = 040 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 127 (t J = 72 Hz 6H) 221 (s 3H) 359 (s 2H) 360 (s 2H) 422 (q J = 72 Hz 4H) 705 (s 1H) 710 (s 1H) 728ndash733 (m 3H) 737ndash740 (m 2H) 13C NMR (150 MHz CDCl3) δ 140 204 402 403 605 617 1255 1266 1280 1292 1341 1375 1391 1408 1421 1717 IR (neat) 3057 2980 2935 1733 1244 cmndash1 Anal Calcd for C22H24O4 C 7498 H 686 Found C 7493 H 699 Diethyl 56-Diphenyl-1H-indene-22(3H)-dicarboxylate (5af) Colorless solids Rf = 039 (hexaneEtOAc 41) 1H NMR (600 MHz CDCl3) δ 1281 (t J = 72 Hz 3H) 1282 (t J = 72 Hz 3H) 368 (s 4H) 4240 (q J = 72 Hz 2H) 4241 (q J = 72 Hz 2H) 709ndash711 (m 4H) 715ndash720 (m 6H) 725 (d J = 06 Hz 2H) 13C NMR (150 MHz CDCl3) δ 140 403 605 618 1263 1278 1299 1394 1396 1416 1717 IR (KBr) 3057 2985 2903 1732 1708 cmndash1 General Procedure for Cyclization of Diyne 4b and Alkyne 1f To a solution of RhCl3bull3H2O (11 mg 004 mmol) and i-Pr2NEt (26 μL 015 mmol) in i-PrOH (20 mL) were added diphenylacetylene 1f (900 mg 50 mmol) and diyne 4b (132 mg 050 mmol) in i-PrOH (30 mL) The mixture was stirred at reflux for 24 h After being cooled to room temperature the reaction mixture was concentrated under reduced pressure The residue was purified by column chromatography on silica gel (hexaneEtOAc 51) to afford 47-dimethyl-56-diphenyl-indan-22-dicarboxylic acid diethyl ester 5bf (102 mg 46) and 45 of 4b was recovered
Diethyl 47-Dimethyl-56-diphenyl-1H-indene-22(3H)-dicarboxylate (5bf) Red liquid Rf = 050 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 132 (t J = 72 Hz 6H) 200 (s 6H) 369 (s 4H) 428 (q J = 72 Hz 4H) 692 (d J = 72 Hz 4H) 704ndash706 (m 2H) 710ndash712 (m 4H) 13C NMR (150 MHz CDCl3) δ 137 192 307 644 1182 1280 1288 1302 1344 1445 1671 IR (neat) 3056 3021 2981 2935 1733 1242 cmndash1 Reference 1 Bhar S Chaudhuri K S Sahu S G Panja C Tetrahedron 2001 57 9011ndash9016 2 Diercks R tom Dieck H Z Naturforsch B Chem Sc 1984 39B 180ndash184 3 Sigman M S Fatland A W Eaton B E J Am Chem Soc 1998 120 5130ndash5131 4 Mori N Ikeda S Odashima K Chem Commun 2001 181ndash182 5 Li J Jiang H Chen M J Org Chem 2001 66 3627ndash3629 6 Rodriacuteguez J G Lafuente A Martiacuten-Villamil R J Polym Sci Part A Polym Chem 2005 43 1228ndash1237 7 Yasuda M Kojima R Tsutsui H Utsunomiya D Ishii K Jinnouchi K Shiragami T J Org Chem 2003 68 7618ndash7624 8 Tagliatesta P Floris B Galloni P Leoni A DrsquoArcangelo G Inorg Chem 2003 42 7701ndash7703 9 Tanaka K Toyoda K Wada A Shirasaki K Hirano M Chem Eur J 2005 11 1145ndash1156 10 Kanner C B Pandit U K Tetrahedron 1982 38 3597ndash3604 11 Hilt G Vogler T Hess W Galbiati F Chem Commun 2005 1474ndash1475
PhPh
PhCO2EtEtO2C
EtO2C
2a
PhPh
PhCO2EtEtO2C
EtO2C
2a
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhMeMe
Me
2c
PhPh
PhMeMe
Me
2c
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeCO2Et
CO2EtMeMe
EtO2C
3d
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
Diethyl 47-Dimethyl-56-diphenyl-1H-indene-22(3H)-dicarboxylate (5bf) Red liquid Rf = 050 (hexaneEtOAc 51) 1H NMR (600 MHz CDCl3) δ 132 (t J = 72 Hz 6H) 200 (s 6H) 369 (s 4H) 428 (q J = 72 Hz 4H) 692 (d J = 72 Hz 4H) 704ndash706 (m 2H) 710ndash712 (m 4H) 13C NMR (150 MHz CDCl3) δ 137 192 307 644 1182 1280 1288 1302 1344 1445 1671 IR (neat) 3056 3021 2981 2935 1733 1242 cmndash1 Reference 1 Bhar S Chaudhuri K S Sahu S G Panja C Tetrahedron 2001 57 9011ndash9016 2 Diercks R tom Dieck H Z Naturforsch B Chem Sc 1984 39B 180ndash184 3 Sigman M S Fatland A W Eaton B E J Am Chem Soc 1998 120 5130ndash5131 4 Mori N Ikeda S Odashima K Chem Commun 2001 181ndash182 5 Li J Jiang H Chen M J Org Chem 2001 66 3627ndash3629 6 Rodriacuteguez J G Lafuente A Martiacuten-Villamil R J Polym Sci Part A Polym Chem 2005 43 1228ndash1237 7 Yasuda M Kojima R Tsutsui H Utsunomiya D Ishii K Jinnouchi K Shiragami T J Org Chem 2003 68 7618ndash7624 8 Tagliatesta P Floris B Galloni P Leoni A DrsquoArcangelo G Inorg Chem 2003 42 7701ndash7703 9 Tanaka K Toyoda K Wada A Shirasaki K Hirano M Chem Eur J 2005 11 1145ndash1156 10 Kanner C B Pandit U K Tetrahedron 1982 38 3597ndash3604 11 Hilt G Vogler T Hess W Galbiati F Chem Commun 2005 1474ndash1475
PhPh
PhCO2EtEtO2C
EtO2C
2a
PhPh
PhCO2EtEtO2C
EtO2C
2a
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhMeMe
Me
2c
PhPh
PhMeMe
Me
2c
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeCO2Et
CO2EtMeMe
EtO2C
3d
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
PhPh
PhCO2EtEtO2C
EtO2C
2a
PhPh
PhCO2EtEtO2C
EtO2C
2a
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhMeMe
Me
2c
PhPh
PhMeMe
Me
2c
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeCO2Et
CO2EtMeMe
EtO2C
3d
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
PhPh
PhCO2EtEtO2C
EtO2C
2a
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhMeMe
Me
2c
PhPh
PhMeMe
Me
2c
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeCO2Et
CO2EtMeMe
EtO2C
3d
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhMeMe
Me
2c
PhPh
PhMeMe
Me
2c
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeCO2Et
CO2EtMeMe
EtO2C
3d
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
PhPh
PhCO2MeMeO2C
MeO2C
2b
PhPh
PhMeMe
Me
2c
PhPh
PhMeMe
Me
2c
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeCO2Et
CO2EtMeMe
EtO2C
3d
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
PhPh
PhMeMe
Me
2c
PhPh
PhMeMe
Me
2c
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeCO2Et
CO2EtMeMe
EtO2C
3d
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
PhPh
PhMeMe
Me
2c
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeCO2Et
CO2EtMeMe
EtO2C
3d
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeCO2Et
CO2EtMeMe
EtO2C
3d
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
MeMe
MeCO2EtEtO2C
EtO2C
2d
MeCO2Et
CO2EtMeMe
EtO2C
3d
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
MeCO2Et
CO2EtMeMe
EtO2C
3d
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
MeCO2Et
CO2EtMeMe
EtO2C
3d
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
PrPr
PrPrPr
Pr
2e
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
PrPr
PrPrPr
Pr
2e
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
PhPh
PhPhPh
Ph
2f
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
PhPh
PhPhPh
Ph
2f
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
CO2MeCO2Me
CO2MeCO2MeMeO2C
MeO2C
2g
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
2h
S
S
SS
S
S
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
2h
S
S
SS
S
S
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
2i
S
S
SS
S
S
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
2i
S
S
SS
S
S
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
2j
S
S
SS
S
S
Ac
Ac
Ac
Ac
Ac
Ac
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
2k
S
S
S
S
S
S
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
2k
S
S
S
S
S
S
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
Ph
Ph
2l
PhH
H H
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
Ph
Ph
2l
PhH
H H
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
p-Tol
p-Tol
2m
p-TolH
H H
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
p-Tol
p-Tol
2m
p-TolH
H H
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
Hex
Hex
2n
HexH
H H
H
H
HexH
Hex Hex
3n
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
CO2Et
CO2Et
2o
CO2EtH
H H
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
CO2Et
CO2Et
2o
CO2EtH
H H
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
H
H
3o
CO2EtH
EtO2C CO2Et
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
H
H
3o
CO2EtH
EtO2C CO2Et
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5al
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Hex
5an
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5aa
CO2Et
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5ac
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5af
Ph
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
EtO2CEtO2C
Ph
5bf
Ph
Me
Me
