Eur. J. Org. Chem. 2007 · © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2007 · ISSN 1434–193X

SUPPORTING INFORMATION

Title: DFT Study on the SnII-Catalyzed Diastereoselective Synthesis of Tetrahydrofuran from D–A Cyclopropane and Benzaldehyde Author(s): Jinsheng Zhang, Wei Shen, Ming Li* Ref. No.: O200700216

LUMO (E = -2.2 e.v.) LUMO-1 (E = -1.3 e.v.) LUMO-2 (E = -0.6 e.v.)

Figure S2. The molecular orbital 3D views, energies and hybridizations of the Sn(OTf)2.

(ΨLUMO = 0.886(p)Sn; ΨLUMO-1 = 0.911(p)Sn; ΨLUMO-2 = 0.827(sp11.0)Sn).

C(1)

C(2 )

H(2) H(1)

H(3)

O(1)O(2)

O(3)O(4)

C(4)C(5)

C(3 )

C(6)

1.2 34

1.4701.3821.490

1.538

1.499

1.495

1.234

1.471

C(1)-C(2): 1. 562C(2)-C(3): 1. 497C(5)-O(4): 1.375C(1)-C(2)-C(3): 60. 3C(2)-C(3)-C(1): 61. 9C(2)-C(1)-C(3): 57. 8C(2)-C(3)-C(1)-C(4): -108.6H(3)-C(2)-C(3)-C(1): 101.2C(6)-C(2)-C(3)-C(1): -109.7

1.086

125.9

S(1)

S(2)O(6)

O(7)

O(10)

O(8)

O(9)O(11)

2.213

2. 359 2.375

2.001

1.7 17

1.6911.688

1 .714

1 .611

2. 224

O(6)-Sn-O(7): 87.8O(6)-Sn-O(10): 67.0O(7)-Sn-O(11): 67.2

100.6100.5

1.612

O(6)-S(1)-O(10): 96.6O(7)-S(1)-O(11): 96.1O(10)-Sn-O(11): 134 .4

O(5 )H(4) C(7)

C(8)

1.24 21.106

1.473

R1 (µ = 3.296) R2 (µ = 3.668) CAT (µ = 3.586)

Figure S1. The structures and electrostatic pictures of the R1, R2 and CAT. (CF3SO3 and C6H5 are represented in sticks for

clarity, bond distances in Å, angles and dihedral angels in degree, moment dipoles, µ, in Debye).

Tb1 (µ = 13.854) Tc1 (µ = 13.163) Mb1 (µ = 11.147)

Tb2 (µ = 9.321) Mb2 (µ = 8.302)

Figure S3. The geometries and parameters of the stationary points in the reactions of Mb and Mc with R2 (CF3SO3 and C6H5

were represented in sticks, bond distances in Å, angles and dihedral angels in degree, dipole moments, µ, in Debye).

O(10)

O(4)

O(5)

1.704

2.312

2.289

C(7)1.458

1.260

1.433

2.226H(4)

O(7)

O(2)

C(2)

2.366

S(2)

C(4)

2.140

C(1)-C(3): 1 .522C(2)-C(3): 1 .494C(1)-C(4): 1 .417C(1)-C(5): 1 .418O (1)-C(4): 1 .294O (2)-C(5): 1 .279Sn-O (2): 2.132Sn-O (6): 2.126Sn-O (7): 2.140O (1)-Sn-O (2): 74 .4O (6)-Sn-O (7): 95 .4

C(6)

C(1)C(2)

O(5)

O(2) O(6)

2.123

2.169

1.262

2.327 2.158C(1)-C(3): 1.520C(2)-C(3): 1.501C(1)-C(4): 1.416O(1)-C(4): 1.288O(2)-C(5): 1.295Sn-O(1): 2.258Sn-O(2): 2.169Sn-O(7): 2.189C(1)-C(3)-C(2): 100.7O(1)-Sn-O(2): 75.3O(6)-Sn-O(7): 77.6

O(8)

O(7)

O(1)

O(2)

O(4)

O(5)

S(2)

C(1)C(2)

2.154

1.8382.151

1.285C(7)

1.502

1.4211.304

1.539 1.368 1.479

C(1)-C(3): 1.508C(2)-C(3): 1.545Sn-O(2): 2.276Sn-O(6): 2.161O(6)-Sn-O(7): 82.5

1.298

1.417

O(7)

O(2)

O(5)

C(2)O(10)

2.130 2.122 C(1)-C(3): 1.523C(3)-C(2): 1.552C(2)-O(5): 1.478O(5)-C(7): 1.371C(1)-C(4): 1.455C(1)-C(5): 1.467Sn-O(1): 2.210Sn-O(2): 2.392Sn-O(6): 2.134H(4)-O(10): 2.474O(1)-Sn-O(2): 71.4O(6)-Sn-O(7): 63.8O(6)-Sn-O(2): 77.5

O(1)

O(5)C(1)

C(2)

2.239

2.089

2.476

1.2511.343

1.706

1.971

1.972

1.488

1.508 1.511

1.096C(6)

C(7)

O(7)

1.466O(4)

O(6)

1.516 S(1)

S(2)

Sn-O(6): 2.110C(1)-C(3): 1.569C(3)-C(2): 1.547O(5)-C(7): 1.440C(7)-C(1): 1.667O(1)-Sn-O(2): 69.1O(6)-Sn-O(7): 86.7O(6)-Sn-O(2): 78.7

Td1 (µ = 18.152) Md1 (µ = 11.749) Td2 (µ = 10.576)

Md2 (µ = 9.357) Td3 (µ = 22.404) Md3 (µ = 9.646)

Figure S4. The geometries and parameters of the stationary points in the reaction of Md with R2 (CF3SO3 and C6H5 were

represented in sticks for clarity, bond distances in Å, angles and dihedral angels in degree, dipole moments, µ, in Debye).

C(1)-C(2)-C(3): 37.5C(1)-C(3)-C(2): 106.3O(5)-C(2)-C(3)-C(1): 142.6C(2)-C(3)-C(1)-C(4): -75.7

C(1)-C(3): 1.508C(3)-C(2): 1.540O(5)-C(7): 1.301C(2)-C(3)-C(1)-C(4): 72.7

C(1)-C(7): 2.122C(3)-C(2): 1.552C(7)-C(8): 1.459Sn-O(7): 2.124O(1)-Sn-O(2): 71.1O(6)-Sn-O(7): 86.2O(7)-Sn-O(1): 77.1C(1)-C(3)-C(2): 109.5C(3)-C(2)-O(5): 102.3C(2)-O(5)-C(7): 113.7C(2)-C(3)-C(1)-C(4): 86.8

Sn-O(6): 2.083Sn-O(7): 2.086C(1)-C(7): 1.659C(2)-C(3): 1.544C(2)-O(5): 1.466O(1)-Sn-O(2): 68.8O(6)-Sn-O(7): 86.8O(7)-Sn-O(1): 79.2C(2)-C(3)-C(1)-C(4): 93.8

Sn-O(2): 2.157Sn-O(7): 2.144C(1)-C(3): 1.504C(2)-C(3): 1.479O(1)-Sn-O(2): 75.0O(6)-Sn-O(7): 80.0O(7) Sn-O(1): 81.3C(1)-C(2)-C(3): 32.6C(2)-C(1)-C(3): 32.0C(1)-C(3)-C(2): 115.4O(5)-C(2)-C(3)-C(1): -98.0

Sn-O(7): 2.096C(1)-C(3): 1.553C(3)-C(2): 1.555C(2)-O(5): 1.481O(5)-C(7): 1.440C(7)-C(1): 1.618O(1)-Sn-O(2): 69.9O(6)-Sn-O(7): 85.6O(7)-Sn-O(1): 78.7

Te1 (µ = 23.006) Me1 (µ = 10.819) Te2 (µ = 10.568)

Me2 (µ = 10.699) Te3 (µ = 24.088) Me3 (µ = 25.695)

Te4 (µ = 15.865) Me4 (µ = 7.676) Te5 (µ = 24.697)

Me5 (µ = 10.007) P1 (µ = 0.864) P2 (µ = 0.861)

Figure S5. The geometries and parameters of the stationary points in the reaction of Me with R2 (CF3SO3 and C6H5 were

represented in sticks for clarity, bond distances in Å, angles and dihedral angels in degree, dipole moments, µ, in Debye).

O(5)-C(2)-C(3)-C(1): 154.2C(2)-C(3)-C(1)-C(4): -79.0

Sn-O(1): 2.164Sn-O(7): 2.126C(2)-C(3): 1.502C(1)-C(3)-C(2): 105.8O(1)-Sn-O(2): 74.4O(6)-Sn-O(7): 79.2

C(3)-C(2): 1.538O(5)-C(7): 1.304Sn-O(6): 2.212Sn-O(7): 2.171O(1)-Sn-O(2): 75.3O(6)-Sn-O(7): 74.0C(2)-C(3)-C(1)-C(4): 63.7

C(1)-C(7): 2.139C(3)-C(2): 1.552O(5)-C(7): 1.370O(1)-Sn-O(2): 70.9O(6)-Sn-O(7): 80.7C(2)-C(3)-C(1)-C(4): 87.5

Sn-O(7): 2.111C(2)-C(3): 1.554C(2)-O(5): 1.464O(5)-C(7): 1.439C(1)-C(7): 1.651

Sn-O(6): 2.135Sn-O(7): 2.132C(1)-C(3): 1.509C(2)-O(5): 1.621C(1)-C(3)-C(2): 114.0

Sn-O(1): 2.160Sn-O(2): 2.351Sn-O(7): 2.132C(1)-C(3): 1.517C(2)-C(3): 1.482O(1)-Sn-O(2): 74.6O(6)-Sn-O(7): 79.0C(1)-C(2)-C(3): 34.7C(1)-C(3)-C(2): 111.5

O(6)-Sn-O(7): 87.4C(1)-C(7): 2.340C(1)-C(3): 1.506C(2)-O(5): 1.474C(2)-C(6): 1.525C(7)-C(8): 1.456Sn-O(6): 2.096Sn-O(7): 2.097

C(1)-C(2): 2.522C(1)-C(3): 1.514C(3)-C(2): 1.480C(2)-C(6): 1.424Sn-O(7): 2.126O(1)-Sn-O(2): 74.6O(6)-Sn-O(7): 79.3O(7)-Sn-O(1): 91.1O(5)-C(2)-C(3)-C(1): -35.3

Sn-O(2): 2.510C(1)-C(7): 1.606C(2)-C(3): 1.557C(2)-O(5): 1.483O(5)-C(7): 1.452O(6)-Sn-O(7): 104.5

Sn-O(1): 2.237Sn-O(7): 2.092C(1)-C(3): 1.561C(1)-C(7): 1.647C(2)-O(5): 1.479O(1)-Sn-O(2): 69.6O(6)-Sn-O(7): 85.6

C(1)-C(3): 1.554C(3)-C(2): 1.542C(2)-O(5): 1.470O(5)-C(7): 1.454C(7)-C(1): 1.611

C(1)-C(3): 1.554C(3)-C(2): 1.542C(2)-O(5): 1.470O(5)-C(7): 1.454C(7)-C(1): 1.611

-220

-200

-180

-160

-140

-120

-100

-80

-60

-40

-20

0

20

-196.2-210.6

-156.3

-185.9

-164.2

-206.3

-178.2

-150.9-157.6

(a) B3LYP/6-311G(d,p) (b) B3LYP/6-31G (c) B3LYP/6-311G(d,p)//B3LYP/6-31G

The

rela

tive

ener

gies

∆E

(k

J·m

ol-1)

R1+R2+CAT

Ma1+R2 Ta1 Ma2 Ta2 Ma3

-119.1 -132.4

-148.3

-134.3

-220

-200

-180

-160

-140

-120

-100

-80

-60

-40

-20

0

20

-152.5-159.8

-156.2

-113.4-113.1

-148.0-154.2

-148.3

-162.4

-150.9-157.6

(a) B3LYP/6-311G(d,p) (b) B3LYP/6-31G (c) B3LYP/6-311G(d,p)//B3LYP/6-31G

The

rela

tive

ener

gies

∆E

(k

J·m

ol)

R1+CAT

Ma Mb Mc Md Me

-119.1-116.9

-152.9

-123.3

Figure S6. The comparison of the relative energies for selected species based on the different calculation levels (a:

optimized at the B3LYP/6-311G** level; b: optimized at the B3LYP/6-31G level; c: the B3LYP/6-311G** single point

energies based on the B3LYP/6-31G optimized structures).

-3 -2 -1 0 1 2 3-3075.637

-3075.636

-3075.635

-3075.634

-3075.633

-3075.632

-3075.631

MeO

OMe

O

OH

PhO

H

R

*Sn

OTf

OTf

MeO

OMe

O

O

H

PhO

H

R

**

Sn

OTf

OTf

OMe

MeO

O

OSn

HPh

O

H

R OTf

OTfE /

Har

tree

Ta2

Ma1

Ma2

Figure S7. The Ta2 intrinsic reaction coordinate

Table S2. The selected NBO energies, E(hartree) and occupied electrons, q(in the parenthesis, unit in e) of D-A

cyclopropanes

NBOs R1 Ma Mb Mc Md Me

σ(C1-C2) -0.5294

(1.8916)

-0.5122

(1.8114)

-0.5176

(1.8213)

-0.5002

(1.8015)

-0.5259

(1.8289)

-0.5272

(1.8308)

σ*(C1-C2) 0.2679

(0.0564)

0.1722

(0.0837)

0.1720

(0.0809)

0.1561

(0.0891)

0.1669

(0.0820)

0.1682

(0.0815) In R2, for NBO of π(O5-C7), E= -0.3728, q=1.9763; for NBO of π*

(O5-C7), E= -0.0168, q=0.1184; for NBO of LP(O5), E= -0.2656,

q=1.8980.

Table S3. The energy gaps (× 2625.5 kJ·mol-1) of the interactional NBOs in the different mechanisms.

Mechanism R1 Ma Mb Mc Md Me

SN2 0.5335 0.4378 0.4376 0.4217 0.4325 0.4338

2πs+2σa 0.6407 0.5450 0.5448 0.5289 0.5397 0.5410

SE2 0.5126 0.4954 0.5008 0.4834 0.5091 0.5104

Table S1. Occupied electrons q(e), bond bending deviation angles θ (˚), Wiberg bond orders Pij, electron density ρ(e·Å-3) at

BCPs and dipole moments µ(Debye) of the bonds of cyclopropane.

Species C1-C2 C1-C3 C2-C3 Species C1-C2 C1-C3 C2-C3

R1 q 1.8917 1.9104 1.9610 Mc q 1.8071 1.8931 1.9654

(0.1667) θ 22.9 22.3 23.3 (0.1555) θ 25.7 25.0 21.6

Pij 0.8809 0.9121 1.0098 Pij 0.7586 0.8888 1.0414

ρ 0.1975 0.2088 0.2309 ρ 0.1624 0.2052 0.2432

µ 2.026 1.989 1.825 µ 2.880 1.881 1.701

Ma q 1.8171 1.8922 1.9643 Md q 1.8323 1.8932 1.9635

(0.1585) Pij 0.7743 0.8903 1.0354 (0.1594) Pij 0.7933 0.8926 1.0313

θ 24.1 20.9 22.9 θ 21.5 21.0 23.0

ρ 0.1681 0.2089 0.2411 ρ 0.1705 0.2090 0.2401

µ 2.741 1.870 1.736 µ 2.560 1.868 1.758

Mb q 1.8254 1.8900 1.9652 Me q 1.8343 1.8912 1.9636

(0.1585) Pij 0.7850 0.8849 1.0389 (0.1596) Pij 0.7961 0.8904 1.0316

θ 24.0 21.2 22.5 θ 24.4 20.8 23.0

ρ 0.1699 0.2035 0.2421 ρ 0.1710 0.2085 0.2403

µ 2.668 1.928 1.735 µ 2.535 1.875 1.764 The numbers in the parentheses are the electron density ρ(r) at the ring critical points (RCPs) of C(1)-C(2)-C(3).

Table S4. The APT charges δ of the species in the Sn(OTf)2-catalyzed cycloaddition reaction of D-A cyclopropane with

benzaldehyde

Species Sn C(1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) O(1) O(2) O(5)

R1 — -0.407 0.166 0.060 1.153 0.988 0.053 — — -0.679 -0.609 —

R2 — — — — — — — 0.864 -0.293 — — -0.663

Ma 1.984 -0.789 0.488 0.122 1.300 1.159 -0.069 — — -0.943 -0.919 —

Mb 1.978 -0.767 0.477 0.108 1.364 1.099 -0.070 — — -1.035 -0.874 —

Mc 1.930 -0.772 0.515 0.087 1.291 1.148 -0.098 — — -0.946 -0.964 —

Md 1.957 -0.761 0.447 0.158 1.297 1.148 -0.047 — — -0.949 -0.973 —

Me 1.992 -0.771 0.453 0.163 1.346 1.115 -0.038 — — -1.022 -0.909 —

Ta1 1.878 -1.000 1.528 -0.025 1.315 1.324 -0.474 1.057 -0.484 -1.018 -1.023 -1.184

Ma1 1.863 -0.783 0.681 0.083 1.107 1.380 -0.069 1.124 -0.546 -0.953 -0.977 -0.943

Ta2 1.961 -0.807 0.634 0.002 1.031 1.294 -0.027 1.364 -0.362 -0.935 -0.948 -0.995

Ma2 1.963 -0.451 0.603 0.003 1.057 1.159 -0.008 0.775 -0.062 -0.903 -0.932 -0.817

Ta3 1.800 -0.684 1.331 -0.040 1.256 1.317 -0.579 1.009 -0.477 -0.947 -0.961 -1.085

Ma3 1.805 -0.781 0.603 0.052 1.381 1.086 -0.039 1.250 -0.506 -0.966 -0.957 -0.943

Ta4 1.827 -0.777 0.632 -0.009 1.344 1.065 -0.028 1.354 -0.367 -0.949 -0.931 -1.016

Ma4 1.901 -0.438 0.571 -0.009 1.159 1.077 0.010 0.794 -0.081 -0.926 -0.906 -0.824

Ta5 1.874 -0.711 1.247 -0.089 1.213 1.218 -0.567 0.878 -0.431 -0.944 -0.948 -0.917

Ma5 1.838 -0.756 0.892 0.055 1.277 1.309 -0.165 1.088 -0.553 -0.948 -0.933 -0.988

Ta6 1.916 -0.825 0.644 0.042 1.067 1.279 -0.080 1.357 -0.418 -0.921 -0.938 -0.954

Ma6 1.943 -0.338 0.521 -0.024 1.081 1.152 0.021 0.710 -0.048 -0.862 -0.934 -0.777

Tb1 1.850 -0.998 1.417 -0.035 1.395 1.282 -0.524 1.021 -0.465 -1.061 -1.034 -1.083

Tc1 1.765 -0.924 1.446 -0.034 1.315 1.317 -0.510 1.054 -0.487 -1.002 -1.007 -1.171

Mb1 1.779 -0.789 0.700 0.099 1.216 1.374 -0.062 1.117 -0.566 -0.991 -1.010 -0.976

Tb2 1.918 -0.784 0.631 0.027 1.098 1.293 -0.014 1.325 -0.372 -0.987 -0.972 -1.007

Mb2 1.979 -0.451 0.593 0.031 1.084 1.131 -0.008 0.772 -0.089 -0.968 -0.911 -0.815

Td1 1.938 -0.959 1.507 -0.054 1.259 1.379 -0.512 1.063 -0.497 -1.091 -1.137 -1.109

Md1 1.734 -0.760 0.769 0.098 1.318 1.279 -0.030 1.090 -0.564 -0.978 -0.987 -0.995

Td2 1.919 -0.777 0.635 0.027 1.299 1.097 -0.015 1.309 -0.362 -0.975 -0.989 -1.007

Md2 1.961 -0.427 0.595 0.028 1.145 1.112 -0.011 0.748 -0.073 -0.914 -0.977 -0.820

Td3 1.934 -0.815 1.418 -0.108 1.226 1.414 -0.568 0.979 -0.469 -1.048 -1.108 -1.028

Md3 1.941 -0.362 0.530 -0.017 1.079 1.163 0.022 0.724 -0.044 -0.892 -0.955 -0.791

Te1 1.976 -0.971 1.618 0.046 1.323 1.350 -0.424 1.150 -0.562 -1.151 -1.098 -1.318

Me1 1.715 -0.769 0.755 0.103 1.335 1.300 -0.037 1.120 -0.561 -0.999 -0.973 -1.021

Te2 1.836 -0.798 0.618 0.030 1.315 1.084 -0.008 1.353 -0.397 -0.979 -0.935 -1.001

Me2 1.887 -0.458 0.591 0.042 1.166 1.025 -0.007 0.780 -0.090 -0.959 -0.872 -0.803

Te3 1.990 -0.973 1.223 -0.039 1.506 1.033 -0.441 0.849 -0.337 -1.113 -1.020 -0.857

Me3 1.883 -0.827 1.023 -0.008 1.468 1.251 -0.206 1.159 -0.496 -1.065 -1.020 -0.939

Te4 1.880 -0.707 0.558 -0.026 1.186 1.253 -0.005 1.331 -0.312 -0.972 -0.922 -0.956

Me4 1.912 -0.294 0.499 -0.038 1.157 1.126 0.054 0.665 -0.074 -0.749 -0.892 -0.760

Te5 1.929 -0.806 1.367 -0.169 1.403 1.182 -0.592 0.982 -0.443 -1.071 -1.017 -0.982

Me5 1.963 -0.415 0.622 -0.021 1.184 1.059 -0.017 0.767 -0.058 -0.963 -0.898 -0.824

In Sn(OTf)2, Sn:1.494, O(6):-0.781, O(7):-0.775, O(10):-0.752, O(11):-0.738,S(1):1.235.

Table S5. The relative energies ∆E (kJ·mol-1), relative Gibbs free energies ∆G (kJ·mol-1), solvation energies ∆Gsol (kJ·mol-1),

and the first two frequencies ν (cm-1) for the intermediates and products

Gas phase In CH2Cl2 a Frequencies Species

a∆G b∆E a∆G b∆G a∆Gsol b∆Gsol ν1 ν2

R1 + R2 + CAT 0.0 0.0 0.0 0.0 -13.0 -9.7 — — c Ma -89.5 -150.9 -110.1 -110.1 12.2 16.0 5.5 17.3 c Mb -88.8 -156.2 -108.2 -116.2 10.0 15.2 10.5 16.5 c Mc -94.1 -162.4 -105.4 -113.7 19.3 23.8 7.3 11.9 c Md -82.1 -152.5 -111.0 -120.9 2.4 6.8 10.9 17.8 c Me -83.0 -154.2 -109.7 -121.4 4.0 8.0 14.1 14.4

Ma1 -73.1 -178.2 -132.7 -106.5 19.6 22.3 14.2 16.3

Ma2 -75.3 -196.2 -127.2 -112.8 29.6 34.1 10.7 15.1

Ma3 -70.3 -165.2 -129.8 -95.8 17.0 20.0 13.1 13.8

Ma4 -83.8 -200.7 -131.7 -113.5 33.5 37.9 6.4 10.6

Ma5 -51.0 -156.1 -105.6 -76.3 28.0 30.5 10.7 17.6

Ma6 -75.1 -207.9 -125.4 -122.3 32.4 36.3 12.4 12.6

Mb1 -80.2 -189.5 -136.7 -103.5 26.0 36.7 12.3 20.5

Mb2 -69.1 -206.2 -118.7 -121.0 30.4 35.8 11.1 12.7

Md1 -81.7 -187.6 -123.0 -96.6 38.6 41.7 9.1 14.7

Md2 -69.2 -207.2 -123.4 -122.1 29.9 35.8 11.4 20.9

Md3 -77.1 -213.4 -133.3 -133.4 26.6 30.7 11.9 12.3

Me1 -71.8 -182.0 -119.9 -94.8 34.4 37.9 12.6 17.4

Me2 -57.6 -195.4 -113.0 -114.5 27.0 31.6 12.8 14.1

Me3 4.9 -101.2 -96.4 -75.7 -27.3 -23.7 7.7 12.2

Me4 -59.3 -194.4 -109.2 -103.9 36.6 41.2 15.1 18.2

Me5 -78.2 -213.8 -135.9 -136.9 23.2 27.5 9.3 12.8 d P1 -11.2 -64.7 -45.0 -22.9 2.9 6.1 22.5 30.4 d P2 -11.2 -64.7 -45.1 -23.0 2.8 6.0 22.5 30.4 d P3 -9.1 -62.1 -43.5 -20.1 3.1 6.3 21.4 34.4

a obtained from the B3LYP/6-31G calculations. b obtained from the B3LYP/6-311G(d,p)// B3LYP/6-31 calculations.

Table S6. The relative energies ∆E(kJ·mol-1), relative Gibbs free energies ∆G(kJ·mol-1), solvation energies ∆Gsol(kJ·mol-1) and

the first two frequencies (cm-1) for the transition states

Gas phase In CH2Cl2 Frequencies Species

a ∆G b ∆E a ∆G b ∆G a ∆Gsol b ∆Gsol ν1 ν2

Ta1 -35.0 -132.4 -84.3 -67.4 12.2 15.7 65.1i 6.8

Ta2 -46.8 -164.2 -98.9 -77.9 33.0 36.9 213.6i 14.4

Ta3 -30.1 -111.0 -87.4 -49.2 9.5 12.5 76.9i 10.1

Ta4 -55.7 -163.6 -113.2 -84.4 28.3 32.1 137.1i 15.6

Ta5 -3.7 -93.4 -57.5 -24.9 16.3 19.3 68.7i 7.9

Ta6 -24.7 -136.9 -81.0 -54.7 28.7 32.8 103.7i 13.5

Tb1 -26.6 -119.5 -79.7 -46.8 18.3 23.4 47.1i 8.4

Tc1 -32.8 -136.0 -74.3 -49.1 33.1 37.6 55.4i 11.9

Tb2 -50.2 -180.5 -96.7 -90.4 36.1 40.9 243.4i 14.1

Td1 4.5 -96.8 -60.3 -39.7 3.6 7.9 56.8i 9.7

Td2 -52.8 -181.4 -102.7 -93.6 33.9 38.5 248.1i 15.1

Td3 10.0 -83.9 -67.9 -46.9 -15.3 -12.3 41.5i 8.7

Te1 9.5 -89.4 -78.3 -57.0 -20.3 -16.8 110.4i 8.7

Te2 -37.0 -166.9 -87.0 -79.0 34.6 38.7 241.7i 10.7

Te3 25.4 -68.7 -50.4 -31.5 -16.9 -12.0 103.1i 6.8

Te4 5.6 -100.6 -62.7 -52.55 13.3 7.0 153.2i 5.9

Te5 25.5 -69.1 -52.4 -35.3 -19.4 -15.4 59.4i 8.2

a obtained from the B3LYP/6-31G calculations. b obtained from the B3LYP/6-311G(d,p)// B3LYP/6-31 calculations.

Table S7. The APT charges δ, Wiberg bond orders Pij, and Electron Density ρ(r) at the BCPs for species in the Ma reactions.

atoms δ bonds Pij ρ(r) atoms δ bonds Pij ρ(r)

Ta1 Sn 1.878 C1-C2 0.1577 — Ma1 Sn 1.863 O8-H4 0.0416 0.0302

C1 -1.000 C1-C3 0.9596 0.2270 C(1) -0.783 C1-C3 1.0085 0.2370

C2 1.528 C2-C3 1.0477 0.2452 C(2) 0.681 C2-C3 0.9869 0.2263

C3 -0.025 C2-O5 0.2277 0.0444 C(3) 0.083 C2-O5 0.7476 0.1689

O5 -1.184 O5-C7 1.6552 0.3463 O(5) -0.943 O5-C7 1.3318 0.3046

C7 1.057 C7-C8 1.1194 0.2672 C(7) 1.124 C7-C8 1.2276 0.2817

Ta2 Sn 1.961 C1-C7 0.4289 0.0647 Ma2 Sn 1.963 C1-C7 0.8492 0.1803

C(1) -0.807 C1-C3 1.0015 0.2295 C(1) -0.451 C1-C3 0.9593 0.2131

C(2) 0.634 C2-C3 0.9706 0.2240 C(2) 0.603 C2-C3 0.9775 0.2231

C(3) 0.002 C2-O5 0.8267 0.2001 C(3) 0.003 C2-O5 0.8743 0.2137

O(5) -0.995 O5-C7 1.0971 0.2738 O(5) -0.817 O5-C7 0.9427 0.2407

C(7) 1.364 C7-C8 1.1302 0.2653 C(7) 0.775 C7-C8 1.0155 0.2449

Ta3 Sn 1.800 C1-C2 0.0161 — Ma3 Sn 1.805 O8-H4 0.0287 0.0258

C(1) -0.684 C1-C3 0.9970 0.2445 C(1) -0.781 C1-C3 1.0160 0.2385

C(2) 1.331 C2-C3 1.0662 0.2514 C(2) 0.603 C2-C3 0.9748 0.2231

C(3) -0.040 C2-O5 0.2958 0.0468 C(3) 0.052 C2-O5 0.7701 0.1780

O(5) -1.085 O5-C7 1.6197 0.3421 O(5) -0.943 O5-C7 1.2817 0.2997

C(7) 1.009 C7-C8 1.1220 0.2673 C(7) 1.250 C7-C8 1.2172 0.2802

Ta4 Sn 1.827 C1-C7 0.3679 0.0542 Ma4 Sn 1.901 C1-C7 0.8444 0.1738

C(1) -0.777 C1-C3 1.0121 0.2350 C(1) -0.438 C1-C3 0.9656 0.2167

C(2) 0.632 C2-C3 0.9686 0.2226 C(2) 0.571 C2-C3 0.9806 0.2276

C(3) -0.009 C2-O5 0.8184 0.1967 C(3) -0.009 C2-O5 0.8731 0.2139

O(5) -1.016 O5-C7 1.1210 0.2780 O(5) -0.824 O5-C7 0.9372 0.2359

C(7) 1.354 C7-C8 1.1453 0.2679 C(7) 0.794 C7-C8 1.0161 0.2427

Ta5 Sn 1.874 C1-C2 0.0522 — Ma5 Sn 1.838 C1-C3 1.0035 0.2339

C(1) -0.711 C1-C3 0.9622 0.2229 C(1) -0.756 C2-C3 1.0088 0.2261

C(2) 1.247 C2-C3 1.0662 0.2433 C(2) 0.892 C2-O5 0.7093 0.1534

C(3) -0.089 C2-O5 0.1824 0.0297 C(3) 0.055 O5-C7 1.3683 0.3112

O(5) -0.917 O5-C7 1.6485 0.3452 O(5) -0.988 C7-C8 1.2071 0.2795

C(7) 0.878 C7-C8 1.1101 0.2639 C(7) 1.088 O8-H4 0.0305 0.0238

Ta6 Sn 1.916 C1-C7 0.3046 0.0479 Ma6 Sn 1.943 C1-C7 0.8807 0.1950

C(1) -0.825 C1-C3 1.0123 0.2303 C(1) -0.338 C1-C3 0.9747 0.2235

C(2) 0.644 C2-C3 0.9720 0.2155 C(2) 0.521 C2-C3 0.9869 0.2227

C(3) 0.042 C2-O5 0.8066 0.1892 C(3) -0.024 C2-O5 0.8816 0.2087

O(5) -0.954 O5-C7 1.1601 0.2877 O(5) -0.777 O5-C7 0.9219 0.2324

C(7) 1.357 C7-C8 1.1729 0.2726 C(7) 0.710 C7-C8 1.0147 0.2441

Table S8. The Wiberg bond orders Pij, and Electron Density ρ(r) at BCPs for species in the Mb and Mc reactions with R2.

bonds Pij ρ(r) bonds Pij ρ(r)

Tb1 C1-C2 0.1504 — Tc1 C1-C2 0.1192 —

C1-C3 0.9635 0.2266 C1-C3 0.9679 0.2278

C2-C3 1.0508 0.2453 C2-C3 1.0429 0.2424

C2-O5 0.1856 0.0365 C2-O5 0.2417 0.0460

O5-C7 1.6724 0.3480 O5-C7 1.6501 0.3454

O10-H4 0.0127 0.0143 O11-H4 0.0168 0.0176

Mb1 C1-C3 1.0052 0.2365 Tb2 C1-C7 0.4602 0.0708

C2-C3 0.9929 0.2274 C1-C3 1.0040 0.2297

C2-O5 0.7297 0.1606 C2-C3 0.9676 0.2233

O5-C7 1.3559 0.3060 C2-O5 0.8398 0.2054

C7-C8 1.2209 0.2816 O5-C7 1.0710 0.2682

O10-H4 0.0325 0.0259 C7-C8 1.1305 0.2652

Mb2 C1-C7 0.8547 0.1768 P1 C1-C7 0.9130 0.1995

C1-C3 0.9557 0.2110 C1-C3 0.9676 0.2190

C2-C3 0.9779 0.2262 C2-C3 0.9835 0.2284

C2-O5 0.8804 0.2182 C2-O5 0.8807 0.2171

O5-C7 0.9339 0.2345 O5-C7 0.9197 0.2278

C7-C8 1.0155 0.2424 C7-C8 1.0025 0.2396

Table S9. The Wiberg bond orders Pij, and Electron Density ρ(r) at BCPs for species in the Md reactions with R2.

bonds Pij ρ(r) bonds Pij ρ(r)

Td1 C1-C2 0.1291 — Md1 O9-H4 0.0371 0.0282

C1-C3 0.9483 0.2241 C1-C3 1.0061 0.2365

C2-C3 1.0674 0.2521 C2-C3 0.9917 0.2275

C2-O5 0.2067 0.0372 C2-O5 0.7352 0.1625

O5-C7 1.6581 0.3470 O5-C7 1.3470 0.3052

C7-C8 1.1198 0.2672 C7-C8 1.2305 0.2831

Td2 C1-C7 0.4636 0.0718 Md2 C1-C7 0.8637 0.1792

C1-C3 1.0036 0.2297 C1-C3 0.9557 0.2122

C2-C3 0.9680 0.2234 C2-C3 0.9803 0.2276

C2-O5 0.8402 0.2055 C2-O5 0.8797 0.2177

O5-C7 1.0666 0.2673 O5-C7 0.9275 0.2305

O9-H4 0.0080 0.0110 C7-C8 1.0110 0.2396

Td3 C1-C2 0.0395 — Md3 C1-C7 0.8803 0.1945

C1-C3 0.9995 0.2375 C1-C3 0.9660 0.2191

C2-C3 1.0975 0.2530 C2-C3 0.9871 0.2229

C2-O5 0.1844 0.0341 C2-O5 0.8798 0.2095

O5-C7 1.6673 0.3481 O5-C7 0.9281 0.2353

C7-C8 1.1141 0.2656 C7-C8 1.0103 0.2434

Table S10. The Wiberg bond orders Pij, and Electron Density ρ(r) at BCPs for species in the Me reactions with R2.

bonds Pij ρ(r) bonds Pij ρ(r)

Te1 C1-C2 0.0999 — Me1 C1-C3 1.0060 0.2358

C1-C3 0.9646 0.2301 C2-C3 0.9943 0.2284

C2-C3 1.0399 0.2424 C2-O5 0.7514 0.1688

C2-O5 0.3910 0.0733 O5-C7 1.3277 0.3031

O5-C7 1.5663 0.3378 C7-C8 1.2411 0.2845

C7-C8 1.1613 0.2730 O8-H4 0.0367 0.0274

Te2 C1-C7 0.4532 0.0696 Me2 C1-C7 0.8634 0.1824

C1-C3 1.0041 0.2296 C1-C3 0.9500 0.2079

C2-C3 0.9676 0.2234 C2-C3 0.9747 0.2235

C2-O5 0.8418 0.2061 C2-O5 0.8864 0.2205

O5-C7 1.0730 0.2685 O5-C7 0.9328 0.2355

C7-C8 1.1364 0.2663 C7-C8 1.0159 0.2435

Te3 C1-C2 0.1054 — Me3 C1-C3 0.9964 0.2357

C1-C3 0.9632 0.2284 C2-C3 1.0215 0.2357

C2-C3 1.0855 0.2512 C2-O5 0.6715 0.1410

C2-O5 0.1522 0.0296 O5-C7 1.3861 0.3188

O5-C7 1.6777 0.3530 C7-C8 1.1902 0.2776

C7-C8 1.1088 0.2650 C2-C6 1.0446 0.2465

Te4 C1-C7 0.4027 0.0487 Me4 C1-C7 0.9024 0.1998

C1-C3 1.0250 0.2369 C1-C3 0.9752 0.2235

C2-C3 0.9668 0.2184 C2-C3 0.9844 0.2216

C2-O5 0.8433 0.2020 C2-O5 0.8845 0.2093

O5-C7 1.1113 0.2830 O5-C7 0.9209 0.2283

C7-C8 1.1433 0.2664 C7-C8 0.9965 0.2365

Te5 C1-C2 0.0513 — Me5 C1-C7 0.8613 0.1840

C1-C3 0.9753 0.2310 C1-C3 0.9636 0.2149

C2-C3 1.0986 0.2520 C2-C3 0.9808 0.2246

C2-O5 0.1619 0.0285 C2-O5 0.8683 0.2115

O5-C7 1.6758 0.3512 O5-C7 0.9425 0.2408

C7-C8 1.1086 0.2652 C7-C8 1.0123 0.2440

Table S11. The comparison of the bond lengths under the B3LYP/6-31G and the B3LYP/6-311G(d,p) optimizations (unit in Ǻ).

C1C2

Ph

HO5

C7 H4Ph

O

SnOTf

O

O

CH3

O

CH3

OS

CF3

O

O8SnOTf

OO

CH3

C1

OO

CH3

O6

S

O

O8

CF3

C2

O5

H

Ph

C7

H4

Ph

C2Ph

H3

C1

O5

C7

Ph

H4

C O

Sn(OTf)2

OCO

CH3

OCH3

C2Ph

H3

C1

O5

C7

Ph

H4

C O

Sn(OTf)2

OC

OCH3

OCH3

Ta1 Ma2 Ta2 Ma3

Bond B3LYP/

6-31G

B3LYP/

6-311G** Bond

B3LYP/

6-31G

B3LYP/

6-311G** Bond

B3LYP/

6-31G

B3LYP/

6-311G**

R1 C1-C2 1.562 1.544 Ma2 C1-C3 1.506 1.504 Ma3 C1-C3 1.564 1.553

C1-C3 1.538 1.526 C3-C2 1.541 1.541 C3-C2 1.555 1.553

Ma C1-C2 1.629 1.600 C2-O5 1.542 1.495 C2-O5 1.475 1.435

C1-C3 1.538 1.532 O5-C7 1.303 1.277 O5-C7 1.431 1.399

C3-C2 1.481 1.472 H4-O8 1.900 1.994 C7-C1 1.656 1.637