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(1)

Supporting Information

Stereochemistry of N-Benzoyl-5-substituted-1-benzazepines Revisited:

Synthesis of the Conformationally Biased Derivatives and Revision of the

Reported Structure

Hidetsugu Tabata, Tetsuya Yoneda, Tomohiko Tasaka, Shigekazu Ito, Tetsuta Oshitari, Hideyo

Takahashi, and Hideaki Natsugari*

Contents

1.

Comparison of anti/syn isomers in the

1

H NMR spectra of IIa-c and IIIa-c.

2

2.

1

H NMR analytical data of Ib (major).

4

3.

VT-NMR spectra at elevated temperatures and determination of

∆G

value between

the anti and syn forms for Ia, IIa, and IIIa.

5

4.

VT-NMR spectra of Ib and Ic at lower temperatures.

6

5.

Energy differences between the conformers determined by DFT calculation.

7

6.

Atomic coordinates for the lowest-energy conformers by DFT calculation. 20

7.

Thermal ellipsoid plots (ORTEP drawing) of compounds Ib, Ic, IIc and IIIa. 27

8.

1

H NMR spectra of Ia and IIa measured in CD

3

OD.

28

9.

1

H-,

13

C-, and 2D-NMR (NOESY, COSY, and HMQC) spectra.

29

(2)

1. Comparison of anti/syn isomers in the

1

H NMR spectra of IIa-c and IIIa-c.

Compounds IIa–c:

X : parts per Million : Proton

5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.11.0

Figure S1.

1

H NMR spectra (600 MHz in DMSO-d

6

): (a) IIa, (b) IIb (before separation of the anti/syn

isomers), and (c) IIc. The descriptors a and e are used for the stereochemical arrangement of the proton,

axial and equatorial orientation, respectively. The assignment of the signals from the anti and syn isomers

are shown in blue and red, respectively.

(3)

Compounds IIIa–c:

X : parts per Million : Proton

5.55.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6

Figure S2.

1

H NMR spectra (600 MHz in DMSO-d

6

): (a) IIIa, (b) IIIb (before separation of the anti/syn

isomers), and (c) IIIc. The descriptors a and e are used for the stereochemical arrangement of the proton,

axial and equatorial orientation, respectively. The assignment of the signals from the anti and syn isomers

are shown in blue and red, respectively.Unidentified peaks (presumably originating in the trans isomer) in

IIIb and IIIc are marked by x.

(4)

2.

1

H NMR analytical data of Ib (major):

Chemical shifts and coupling (Table S1), relation of the coupling of the ring protons (Table

S2), and relation between

3

J values and torsion angles (Table S3).

Table S3. Torsion angles and observed vicinal coupling (

3

J)

H

2eq

-C2-C3-H

3eq

H

2eq

-C2-C3-H

3ax

H

3ax

-C3-C4-H

4eq

H

3ax

-C3-C4-H

4ax

H

2ax

-C2-C3-H

3ax

H

2ax

-C2-C3-H

3eq

H

3eq

-C3-C4-H

4eq

H

3eq

-C3-C4-H

4ax

4.1 (H

2eq

, H

3eq

)

45

6.9 (H

2eq

, H

3ax

)

20

9.6 (H

2ax

, H

3ax

)

170

3.4 (H

2ax

, H

3eq

)

50

4.1 (H

3ax

, H

4eq

)

45

9.6 (H

3ax

, H

4ax

)

170

6.9 (H

3eq

, H

4eq

)

20

4.1 (H

3eq

, H

4ax

)

45

H

4eq

-C4-C5-H

5ax

H

4ax

-C4-C5-H

5ax

3

J (Hz)

3.4 (H

4eq

, H

5ax

)

50

10.3 (H

4ax

, H

5ax

)

180

57

61

178

64

64

177

54

65

84

160

torsion angles

(

º

)

by the X-ray analysis

a

torsion angles

(

º

)

by the Karplus equation

b

(5)

3. VT-NMR spectra at elevated temperatures and determination of

∆G

value between

the anti and syn forms for Ia, IIa, and IIIa.

X : parts per Million : Proton

5.45.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7

Figure S3. VT-NMR of Ia.

X : parts per Million : Proton

6.05.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1

Figure S4. VT-NMR of IIa.

∆G

= 68.8 kJ/mol

Tc = 333 K

(in DMSO-d

6

)

∆G

= 69.5 kJ/mol

Tc = 383 K

(in DMSO-d

6

)

(6)

X : parts per Million : Proton 5.55.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7

N

O

llIa

N(CH

3

)

2

373 K

353 K

333 K

313 K

296 K

393 K

Figure S5. VT-NMR of IIIa.

3. VT-NMR spectra of Ib and Ic at lower temperatures.

X : parts per Million : Proton

5.25.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.80.7

Figure S6. VT NMR of Ib.

∆G

= 71.0 kJ/mol

Tc = 353 K

(in DMSO-d

6

)

(7)

X : parts per Million : Proton

5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8

Figure S7. VT-NMR of Ic: Although the signals in the syn isomer of Ic apparently did not show any

change, broadening was observed at around 253 K. See Ref. 15 in the main text.

4. Energy differences between the conformers determined by HF/DFT calculation (Tables S4–

S9).

Conformer generations were performed for Ia, Ib, Ic, IIa, IIc, and IIIa.

Tables S1–S6 show the

energy differences of the conformers in comparison with the lowest-energy conformer determined by

HF/DFT calculation,

s1

i.e.,

∆E values determined using UFF, RHF/6-31G(d,p), RB3LYP/6-31G(d,p),

and B3LYP/6-311+G(d,p) levels, and

∆G values determined using the B3LYP/6-311+G(d,p) level. The

right column of the tables shows the geometry type of the conformers determined using the

B3LYP/6-311+G(d,p) level, and the following abbreviations are used: E (E), Z (Z), anti (A), syn (S), chair (C), and

boat (B), and when the azepine ring adopts the twisted form, (T) is added. For example, the E-anti-boat

conformer is expressed as E-A-B, and if the ring adopts the twisted boat form, E-A-B(T) is used.

(8)

E /kcal/mol

G /hartree

1

54.68569893

-811.950115 -822.055202 -827.379261 -827.564581

-827.279968

2

59.62406095

-811.949121 -822.051453 -827.375004 -827.563219

-827.279903

3

57.68508778

-811.947128 -822.050388 -827.373201 -827.561619

-827.278719

4

55.20289022

-811.95485 -822.059343 -827.382974 -827.568495

-827.284081

5

55.7808022

-811.948322 -822.051284 -827.374461

6

53.32509744

-811.956125 -822.061096 -827.384764

-827.57011

-827.285468

7

57.50274019

-811.949121 -822.051453 -827.375004

8

55.98910529

-811.951321 -822.055583 -827.378968 -827.564289

-827.28044

9

54.4631747

-811.951019 -822.056578 -827.378923 -827.565162

-827.281494

10

58.16834094

-811.951948 -822.055583 -827.378968 -827.564289

-827.280441

11

55.37906371

-811.951474 -822.057824 -827.380535

12

51.78253445

-811.955715 -822.060078 -827.383856 -827.568927

-827.283934

13

60.529411

-811.95485 -822.059343 -827.382974 -827.568495

-827.284081

14

52.4430481

-811.950678

-822.05607 -827.378831 -827.564846

-827.281601

15

59.0056655

-811.945534 -822.048555 -827.372262

16

57.25910214

-811.947178 -822.053389 -827.375981

17

56.80009425

-811.951948 -822.055583 -827.378968 -827.564289

-827.28044

18

59.61750654

-811.947128 -822.050388 -827.373201

19

59.45567545

-811.947128 -822.050388 -827.373201

Table S4-1. Compound Ia

Ia

ID No.

UFF

RHF/STO-3G

RHF/6-31G(d,p)

RB3LYP/6-31G(d,p)

RB3LYP/6-311+G(d,p)

RB3LYP/6-311+G(d,p)

E /hartree

(9)

ΔG (kJ/mol)

1

12.15

15.48

14.45

14.52

14.44

E-A- C(T)

2

32.81

25.32

25.62

18.09

14.61

Z-A- B

3

24.70

28.11

30.36

22.29

17.72

Z-S- B(T)

4

14.31

4.60

4.70

4.24

3.64

E-A- B

5

16.73

25.76

27.05

-

-6

6.45

0.00

2)

0.00

3)

0.00

4)

0.00

5)

E-A- C

6)

7

23.93

25.32

25.62

-

-8

17.60

14.47

15.22

15.28

13.20

E-S- B(T)

9

11.22

11.86

15.34

12.99

10.43

Z-A- C

10

26.72

14.47

15.22

15.28

13.20

E-S- B(T)

11

15.05

8.59

11.10

-

-12

0.00

1)

2.67

2.38

3.10

4.03

E-S- C

13

36.60

4.60

4.70

4.24

3.64

E-A- B

14

2.76

13.20

15.58

13.82

10.15

Z-S- C

15

30.22

32.93

32.82

-

-16

22.91

20.23

23.06

-

-17

20.99

14.47

15.22

15.28

13.20

E-S- B(T)

18

32.78

28.11

30.36

-

-19

32.10

28.11

30.36

-

-1)

E : 51.78253 kcal/mol,

2)

E : –822.06110 hartree (h),

3)

E : –827.38476 h,

4)

E : –827.57011 h,

5)

G : –827.28547 h,

6)

The lowest-energy conformer.

Table S4-2. Compound Ia

Ia

ID No.

UFF

RHF/6-31G(d,p)

RB3LYP/6

-31G(d,p)

RB3LYP/6-311+G(d,p)

Geometry

type of

conformers

(10)

UFF

RHF/STO-3G

RHF/6-31G(d,p)

RB3LYP/6-31G(d,p)

RB3LYP/6-311+G(d,p)

RB3LYP/6-311+G(d,p)

E / kcal/mol

G / hartree

1

52.55487834

-1265.95469 -1280.95278 -1286.97294 -1287.18698

-1286.9135

2

53.58790302

-1265.95386 -1280.95127 -1286.97026 -1287.18488

-1286.91256

3

56.8986252

-1265.95052 -1280.94928

-1286.9681 -1287.18242

-1286.91074

4

55.04186294

-1265.9543 -1280.95249

-1286.971 -1287.18587

-1286.91351

5

53.85309189

-1265.95623 -1280.95464 -1286.97468 -1287.18897

-1286.91577

6

57.97820814

-1265.95052 -1280.94928

-1286.9681 -1287.18242

-1286.91073

7

56.46467779

-1265.94867 -1280.94674 -1286.96738 -1287.18169

-1286.90841

8

59.41211053

-1265.94746

-1280.9462 -1286.96704

9

57.66807419

-1265.95219 -1280.95019 -1286.96908 -1287.18435

-1286.91219

10

58.32609678

-1265.95098 -1280.94807 -1286.96837 -1287.18254

-1286.91022

11

55.77931381

-1265.95515 -1280.95259 -1286.97278 -1287.18733

-1286.91424

12

56.31367214

-1265.95316

-1280.9523 -1286.97192 -1287.18616

-1286.91319

13

61.07394174

-1265.94772 -1280.94928

-1286.9681 -1287.18242

-1286.91073

14

57.34333881

-1265.95092 -1280.94544 -1286.96483

15

57.07733027

-1265.95057 -1280.94807 -1286.96837 -1287.18254

-1286.91022

16

62.33571907

-1265.94362 -1280.95019 -1286.96908 -1287.18435

-1286.91219

Table S5-1. Compound Ib

Ib

ID No.

E / hartree

(11)

UFF

RHF/6-31G(d,p)

RB3LYP/

6-31G(d,p)

ΔE (kJ/mol) ΔG (kJ/mol)

1

0.00

1)

4.88

4.56

5.94

5.94

E-S- C

2

4.32

8.85

11.61

8.42

8.42

Z-S -C

3

18.17

14.07

17.26

13.19

13.19

Z-S- B(T)

4

10.41

5.64

9.65

5.93

5.93

Z-A -C

5

5.43

0.00

2)

0.00

3)

0.00

4)

0.00

5)

E-A- C

6)

6

22.69

14.07

17.26

13.22

13.22

Z-S- B(T)

7

16.36

20.75

19.16

19.31

19.31

E-A- C(T)

8

28.69

22.15

20.06

-

-9

21.39

11.67

14.70

9.39

9.39

Z-A- B

10

24.15

17.25

16.56

14.55

14.55

E-S- B(T)

11

13.49

5.39

4.98

4.01

4.01

E-A- B

12

15.73

6.13

7.24

6.77

6.77

E-A- C

13

35.64

14.07

17.26

13.23

13.23

Z-S- B(T)

14

20.03

24.15

25.87

-

-15

18.92

17.25

16.56

14.56

14.56

E-S- B(T)

16

40.92

11.67

14.70

9.39

9.39

Z-A-B

1)

E : 52.55488 kcal/mol,

2)

E : –1280.95464 hartree (h),

3)

E : –1286.97100 h,

4)

E : –1287.18897 h,

5)

G : –1286.91577 h,

6)

The lowest-energy conformer.

Table S6-2. Compound Ib

Ib

ID No.

RB3LYP/6-311+G(d,p)

Geometry

type of

conformers

ΔE (kJ/mol)

(12)

UFF

RHF/STO-3G

RHF/6-31G(d,p)

RB3LYP/6-31G(d,p)

RB3LYP/6-311+G(d,p)

RB3LYP/6-311+G(d,p)

E / kcal/mol

G / hartree

1

62.31973419

-850.526515 -861.088668 -866.692943 -866.885381

-866.576329

2

66.78961719

-850.523163 -861.080087 -866.685926

3

60.83561199

-850.531478 -861.090647 -866.695596 -866.887636

-866.577609

4

58.01383493

-850.529992 -861.090892 -866.695108 -866.887964

-866.578779

5

64.23707324

-850.52812 -861.087823 -866.693848 -866.885971

-866.575173

6

63.56838203

-850.526366 -861.084415 -866.689722

7

62.49959179

-850.52753 -861.085899 -866.690085

8

57.13266176

-850.535325 -861.094963 -866.700061 -866.891929

-866.581094

9

65.85076001

-850.521764 -861.083187 -866.687964

10

62.091297

-850.527754 -861.088408 -866.694575

-866.8868

-866.577022

11

64.45995532

-850.529092 -861.088317 -866.694203 -866.886415

-866.575735

12

63.435581

-850.531477 -861.090647 -866.695596 -866.887636

-866.577608

13

69.06105839

-850.523163 -861.080087 -866.685926

14

65.10193524

-850.531477 -861.090647 -866.695595 -866.887636

-866.577609

15

65.22364782

-850.531476 -861.090647 -866.695595 -866.887636

-866.577609

16

77.0431382

-850.531477 -861.090647 -866.695595 -866.887636

-866.577609

17

64.823802

-850.52753 -861.085899 -866.690085

Table S6-1. Compound Ic

Ic

ID No.

E / hartree

(13)

UFF

RHF/6-31G(d,p)

RB3LYP/

6-31G(d,p)

ΔE (kJ/mol) ΔG (kJ/mol)

1

21.70

16.53

18.69

17.19

12.51

Z-S- B(T)

2

40.40

39.06

37.11

-

-3

15.49

11.33

11.72

11.27

9.15

E-S- B(T)

4

3.69

10.69

13.00

10.41

6.08

Z-S- C

5

29.72

18.74

16.31

15.64

15.55

E-A- C

6

26.93

27.69

27.14

-

-7

22.46

23.80

26.19

-

-8

0.00

1)

0.00

2)

0.00

3)

0.00

4)

0.00

5)

E-S- C

6)

9

36.48

30.92

31.76

-

-10

20.75

17.21

14.40

13.47

10.69

E-A- C(T)

11

30.66

17.45

15.38

14.48

14.07

E-A- B

12

26.37

11.33

11.72

11.27

9.15

E-S- B(T)

13

49.91

39.06

37.11

-

-14

33.34

11.33

11.72

11.27

9.15

E-S- B(T)

15

33.85

11.33

11.72

11.27

9.15

E-S- B(T)

16

83.31

11.33

11.72

11.27

9.15

E-S- B(T)

17

32.18

23.80

26.19

-

-1)

E : 57.13266 kcal/mol,

2)

E : –861.09496 hartree (h),

3)

E : –866.70006 h,

4)

E : –866.89193 h,

5)

G : –866.58109 h,

6)

The lowest-energy conformer.

Table S6-2. Compound Ic

Ic

ID No.

RB3LYP/6-311+G(d,p)

Geometry

type of

conformers

ΔE (kJ/mol)

(14)

UFF

RHF/STO-3G

RHF/6-31G(d,p)

RB3LYP/6-31G(d,p)

RB3LYP/6-311+G(d,p)

RB3LYP/6-311+G(d,p)

E / kcal/mol

G / hartree

1

56.33224042

-885.785961 -896.914488 -902.596244

2

52.47329769

-885.793541 -896.922509 -902.603784 -902.816705

-902.531377

3

54.84322981

-885.788455 -896.914772 -902.596611

4

51.81741318

-885.792232 -896.920879 -902.601977 -902.815112

-902.529784

5

54.64481958

-885.791256 -896.920035 -902.601096 -902.814471

-902.5294

6

54.99881616

-885.78666 -896.915128

-902.59715

7

56.99279652

-885.784652 -896.910202

-902.59116

8

57.72443143

-885.786326 -896.912877 -902.594471

9

55.95716445

-885.788145 -896.916754

-902.59792

10

56.48272904

-885.786077

-896.91602 -902.597542

11

57.66526401

-885.788455 -896.915129 -902.596444

12

58.89180911

-885.790846 -896.918885 -902.599718

13

55.26071947

-885.789432 -896.921359 -902.602391 -902.814275

-902.5289

14

59.08204476

-885.78576

-896.9129 -902.593807

15

60.40046225

-885.784652 -896.910191 -902.591147

16

56.13801059

-885.785485 -896.911747 -902.592877

17

59.08710526

-885.786077 -896.916021 -902.597543

18

54.74799269

-885.784835 -896.911972 -902.593198

19

56.75711438

-885.787805 -896.917485 -902.598462

20

54.21925051

-885.788828 -896.918823 -902.598543

21

52.87381067

-885.78998 -896.921366

-902.60242 -902.814289

-902.528565

22

62.0619815

-885.786639 -896.908502 -902.591452

23

51.84310211

-885.792232 -896.920893 -902.602019 -902.815127

-902.529889

24

54.44955781

-885.78824 -896.918812 -902.598894

25

62.40836359

-885.786639 -896.908502 -902.591452

Table S7-1. Compound IIa

IIa

ID No.

(15)

UFF

RHF/6-31G(d,p)

RB3LYP/

6-31G(d,p)

ΔE (kJ/mol) ΔG (kJ/mol)

1

18.89

21.06

19.80

-

-2

2.74

0.00

2)

0.00

3)

0.00

4)

0.00

5)

E-A- C

6)

3

12.66

20.31

18.83

-

-4

0.00

1)

4.28

4.74

4.18

4.18

E-S- C

5

11.83

6.50

7.06

5.87

5.19

E-A- B

6

13.31

19.38

17.42

-

-7

21.65

32.31

33.14

-

-8

24.71

25.29

24.45

-

-9

17.32

15.11

15.40

-

-10

19.52

17.04

16.39

-

-11

24.47

19.38

19.27

-

-12

29.60

9.51

10.68

-

-13

14.41

3.02

3.66

6.38

6.50

Z-S- C

14

30.40

25.23

26.20

-

-15

35.91

32.34

33.18

-

-16

18.08

28.26

28.64

-

-17

30.42

17.03

16.39

-

-18

12.26

27.66

27.80

-

-19

20.67

13.19

13.97

-

-20

10.05

9.68

13.76

-

-21

4.42

3.00

3.58

6.34

7.38

Z-A- C

22

42.86

36.78

32.38

-

-23

0.11

4.24

4.63

4.14

3.91

E-A-C

24

11.01

9.71

12.84

-

-25

44.31

36.78

32.38

-

-1)

E : 51.81741 kcal/mol,

2)

E : –896.92251 hartree (h),

3)

E : –902.60378 h,

4)

E : –902.81671 h,

5)

G : –902.53138 h,

6)

The lowest-energy conformer.

Table S7-2. Compound IIa

IIa

ID No.

RB3LYP/6-311+G(d,p)

Geometry

type of

conformers

ΔE (kJ/mol)

(16)

UFF

RHF/STO-3G

RHF/6-31G(d,p)

RB3LYP/6-31G(d,p)

RB3LYP/6-311+G(d,p)

RB3LYP/6-311+G(d,p)

E / kcal/mol

G / hartree

1

58.54328954

-924.366006 -935.947339 -941.908892

2

60.7147015

-924.375884 -935.957472 -941.921788 -942.140084

-941.828118

3

60.01813425

-924.368765 -935.956024

-941.91847 -942.138278

-941.827548

4

64.66746757

-924.368729 -935.951261 -941.914872 -942.134421

-941.824288

5

64.64171699

-924.359815 -935.942066 -941.905118

6

61.86149582

-924.369374 -935.951358 -941.914112 -942.134275

-941.823546

7

60.97155673

-924.369978 -935.952195 -941.915056 -942.134981

-941.823989

8

59.87743387

-924.369507 -935.950573 -941.913664 -942.133912

-941.8235

9

61.47703718

-924.366254 -935.948606 -941.911542

10

62.37709344

-924.364649 -935.949065 -941.910833

11

63.59614201

-924.368729 -935.951261 -941.914872 -942.134421

-941.824285

12

65.03539063

-924.3679 -935.952121 -941.915962 -942.135317

-941.824885

13

64.02493424

-924.359999 -935.942912 -941.905691

14

60.41210162

-924.3679 -935.952121 -941.915962 -942.135317

-941.824885

15

61.80727134

-924.363486 -935.942925 -941.904919

16

60.25080514

-924.366006 -935.947339 -941.908892

17

66.28586551

-924.363005

-935.94228 -941.905162

18

63.52971499

-924.366938 -935.952068 -941.914917 -942.135587

-941.823791

19

64.11696324

-924.363005

-935.94228 -941.905162

20

64.09635064

-924.365005 -935.946854 -941.909954

21

66.55967534

-924.366254 -935.948606 -941.911542

22

58.52025959

-924.366006 -935.947339 -941.908893

Table S8-1. Compound IIc

IIc

ID No.

(17)

UFF

RHF/6-31G(d,p)

RB3LYP/6

-31G(d,p)

ΔE (kJ/mol)

1

0.10

26.61

33.86

-

-2

9.18

0.00

2)

0.00

3)

0.00

4)

0.00

5)

E-S- C

6)

3

6.27

3.80

8.71

4.74

1.50

E-S- C

4

25.72

16.31

18.16

14.87

10.06

E-S- B(T)

5

25.61

40.45

43.77

-

-6

13.98

16.05

20.15

15.25

12.00

E-A- B

7

10.26

13.86

17.67

13.40

10.84

E-A- C

8

5.68

18.12

21.33

16.21

12.12

E-S- B

9

12.37

23.28

26.90

-

-10

16.14

22.07

28.76

-

-11

21.24

16.31

18.16

14.87

10.06

E-S- B(T)

12

27.26

14.05

15.29

12.52

8.49

E-A- C(T)

13

23.03

38.23

42.26

-

-14

7.92

14.05

15.29

12.52

8.49

E-A- C(T)

15

13.75

38.19

44.29

-

-16

7.24

26.61

33.86

-

-17

32.49

39.89

43.65

-

-18

20.96

14.19

18.04

11.81

11.36

Z-S- B(T)

19

23.42

39.89

43.65

-

-20

23.33

27.88

31.07

-

-21

33.64

23.28

26.90

-

-22

0.00

1)

26.61

33.86

-

-ΔG (kJ/mol)

1)

E : 58.52026 kcal/mol,

2)

E : –935.95747 hartree (h),

3)

E : –941.92179 h,

4)

E : –942.14008 h,

5)

G : –941.82812 h,

6)

The lowest-energy conformer.

Table S8-2. Compound IIc

IIc

ID No.

RB3LYP/6-31G(d,p)

Geometry

type of

conformers

ΔE (kJ/mol)

(18)

UFF

RHF/STO-3G

RHF/6-31G(d,p)

RB3LYP/6-31G(d,p)

RB3LYP/6-311+G(d,p)

RB3LYP/6-311+G(d,p)

E / kcal/mol

G / hartree

1

72.68640093

-943.414591

-955.1351747 -961.344078

2

72.91454299

-943.419179

-955.1372586 -961.345269

3

70.88023692

-943.419528

-955.1384229 -961.346167

4

68.01012435

-943.420398

-955.1395597 -961.348056

-961.56233

-961.212497

5

71.91729757

-943.416216

-955.1331036 -961.341504

6

71.63907381

-943.418054

-955.1349576 -961.343598

7

74.84791625

-943.413254

-955.1334442 -961.340859

8

70.14084227

-943.418057

-955.1345809 -961.342773

9

74.53779792

-943.415237

-955.1334745 -961.342649

10

64.0089252

-943.422711

-955.1415636

-961.35034 -961.564939

-961.213716

11

68.83992701

-943.416216

-955.1331036 -961.341504

12

67.85949315

-943.417431

-955.1349371 -961.345081

13

70.74135113

-943.415237

-955.1334745

-961.34266

14

73.16861089

-943.413264

-955.1301457 -961.337822

15

69.37693823

-943.418667

-955.135809 -961.343461

16

80.72924692

-943.416386

-955.1364816

-961.34513

17

76.83043674

-943.414015

-955.1339153 -961.342489

18

75.55026809

-943.416386

-955.1364816 -961.345128

19

67.2471993

-943.423862

-955.1425704 -961.350587 -961.565393

-961.215024

20

67.2185045

-943.418223

-955.13759 -961.344118

21

74.13589705

-943.411644

-955.1310561 -961.339121

22

69.32370674

-943.415369

-955.133599 -961.343116

23

71.45119445

-943.414886

-955.1322675 -961.340424

24

62.83631773

-943.421161

-955.140881

-961.34766 -961.562694

-961.212947

25

70.31989713

-943.41515

-955.1358707

-961.34328

26

74.11782714

-943.415237

-955.1334745 -961.342649

27

68.01810254

-943.423235

-955.1425868 -961.350209 -961.565174

-961.215168

28

68.944487

-943.42224

-955.141096 -961.349542 -961.564221

-961.213918

29

63.7694959

-943.419575

-955.1406368 -961.347683 -961.561524

-961.210377

30

75.53602267

-943.413264

-955.1301457 -961.337822

31

68.35681202

-943.418053

-955.13291 -961.341885

32

72.22698319

-943.411614

-955.1307385 -961.340313

33

71.96478057

-943.418801

-955.1394024 -961.347729 -961.562466

-961.212898

34

75.84170145

-943.413264

-955.1301457 -961.337822

35

71.93923989

-943.418057

-955.1345809 -961.342779

36

72.64430274

-943.415082

-955.1340304 -961.342175

37

74.5627805

-943.415237

-955.1334745 -961.342649

38

66.00259487

-943.423235

-955.1425868 -961.350218 -961.565151

-961.215051

39

76.28065073

-943.410258

-955.1303045 -961.339714

40

70.60406641

-943.417279

-955.1382632 -961.345698

41

72.58632583

-943.415082

-955.1340304 -961.342164

42

79.2204099

-943.41363

-955.1415636 -961.350345 -961.564957

-961.213617

43

70.62488887

-943.416637

-955.1365534

-961.3436

44

72.82102676

-943.415059

-955.1330436 -961.340619

45

75.98114521

-943.412484

-955.1318125 -961.342043

46

75.17396192

-943.41363

-955.1415636 -961.350345 -961.564957

-961.213617

Table S9-1. Compound IIIa

IIIa

ID No.

(19)

UFF

RHF/6-31G(d,p)

RB3LYP/

6-31G(d,p)

ΔE (kJ/mol) ΔG (kJ/mol)

1

41.21

19.46

17.09

-

-2

42.17

13.99

13.96

-

-3

33.66

10.93

11.60

-

-4

21.65

7.95

6.65

8.04

7.01

E-S -C(T)

5

37.99

24.90

23.85

-

-6

36.83

20.03

18.35

-

-7

50.26

24.00

25.54

-

-8

30.56

21.02

20.52

-

-9

48.96

23.92

20.84

-

-10

4.91

2.69

0.65

1.19

3.81

E-S- C

11

25.12

24.90

23.85

-

-12

21.02

20.08

14.46

-

-13

33.07

23.92

20.81

-

-14

43.23

32.66

33.51

-

-15

27.37

17.80

18.71

-

-16

74.86

16.03

14.33

-

-17

58.55

22.77

21.26

-

-18

53.20

16.03

14.33

-

-19

18.46

0.04

0.00

3)

0.00

4)

0.38

E-A- B

20

18.34

13.12

16.98

-

-21

47.28

30.27

30.10

-

-22

27.14

23.60

19.62

-

-23

36.04

27.09

26.68

-

-24

0.00

1)

4.48

7.68

7.09

5.83

Z-S- C

25

31.31

17.63

19.18

-

-26

47.20

23.92

20.84

-

-27

21.68

0.00

2)

0.99

0.58

0.00

5)

E-A- C

6)

28

25.56

3.91

2.74

3.08

3.28

E-A- C

29

3.90

5.12

7.62

10.16

12.58

E-S- C

30

53.14

32.66

33.51

-

-31

23.10

25.41

22.85

-

-32

39.29

31.11

26.97

-

-33

38.19

8.36

7.51

7.69

5.96

E-A- C

34

54.41

32.66

33.51

-

-35

38.09

21.02

20.50

-

-36

41.04

22.46

22.08

-

-37

49.06

23.92

20.84

-

-38

13.25

0.00

0.97

0.64

0.31

E-A- C

39

56.25

32.25

28.55

-

-40

32.50

11.35

12.84

-

-41

40.79

22.46

22.11

-

-42

68.55

2.69

0.64

1.15

4.07

E-S- C

43

32.59

15.84

18.34

-

-44

41.78

25.06

26.17

-

-45

55.00

28.29

22.43

-

-46

51.62

2.69

0.64

1.15

4.07

E-S- C

1)

E : 62.83632 kcal/mol,

2)

E : –955.14259 hartree (h),

3)

E : –961.35059 h,

4)

E : –961.56539 h,

5)

G : –961.21517 h,

6)

The lowest-energy conformer.

Table S9-2. Compound IIIa

IIIa

ID No.

RB3LYP/6-311+G(d,p)

Geometry

type of

conformers

ΔE (kJ/mol)

(20)

5. A

tomic coordinates for the lowest-energy conformers by DFT calculation (Tables S10–S16).

Atomic coordinates obtained by the calculation using the RB3LYP/6-311+G(d,p) level are shown

for the lowest-energy conformers. As for the compound IIIa, those of the 2

nd

lowest-energy conformer

is also shown.

Total Energy

Atom

x

y

z

C

0.00000

0.00000

0.00000

C

0.00000

0.00000

1.39390

C

1.20489

0.00000

2.08912

C

2.40103

0.01799

1.37955

C

2.39952

0.01080

-0.01667

C

1.18925

-0.00214

-0.73805

C

1.19976

-0.03903

-2.26480

C

1.75498

1.27119

-2.88213

N

3.64392

0.10254

-0.72141

C

3.88698

1.37615

-1.42704

C

3.28058

1.40975

-2.83089

C

-0.16313

-0.37950

-2.88275

C

4.71070

-0.76384

-0.55848

O

5.83591

-0.47443

-0.94652

C

4.47137

-2.10653

0.08058

C

3.35720

-2.90484

-0.19694

C

3.25098

-4.18007

0.35376

C

4.24669

-4.66321

1.20066

C

5.36307

-3.87409

1.47729

C

5.48231

-2.61060

0.90719

H

-0.95013

-0.00913

-0.51838

H

-0.94164

-0.00203

1.93135

H

1.21736

0.00023

3.17294

H

3.34899

0.04122

1.90403

H

1.89456

-0.83951

-2.55249

H

1.44685

1.31074

-3.93239

H

1.27976

2.12801

-2.38903

H

4.96692

1.50464

-1.48229

H

3.47366

2.18121

-0.81131

H

3.57175

2.35619

-3.30049

H

3.74028

0.61276

-3.42638

H

-0.58476

-1.29741

-2.46502

H

-0.88952

0.42575

-2.73549

H

-0.05224

-0.52423

-3.96022

H

2.57499

-2.54164

-0.85084

H

2.38910

-4.79542

0.12132

H

4.15754

-5.65235

1.63585

H

6.14601

-4.24815

2.12741

H

6.36191

-2.00403

1.08506

Table S10. Ia: ID No. 6 (the lowest energy conformaer)

Gibbs Free Energy

(298.15K, 1 atm)

-827.285468 hartree

(21)

Total Energy

Atom

x

y

z

C

0.00000

0.00000

0.00000

C

0.00000

0.00000

1.39336

C

1.19249

0.00000

2.12040

C

2.41312

-0.00524

1.41072

C

1.19765

-0.02081

-0.70136

C

2.39339

-0.04238

0.00947

C

1.21207

-0.00153

3.64820

C

1.75487

-1.33970

4.21946

C

3.28100

-1.48807

4.17910

C

3.90394

-1.38707

2.78531

C

-0.14486

0.33519

4.28101

C

4.64425

0.86433

2.13867

C

4.37153

2.22806

1.56329

C

5.27190

4.13228

0.36599

C

5.41890

2.84398

0.86711

C

3.18812

2.94040

1.78019

C

4.08580

4.83522

0.58022

C

3.05000

4.24048

1.29654

O

5.74135

0.61935

2.62095

N

3.63794

-0.08853

2.13554

Cl

3.89147

-0.16386

-0.89704

H

-0.93878

0.00796

-0.54188

H

-0.94759

0.00803

1.91518

H

1.21624

-0.03939

-1.78320

H

1.91696

0.78110

3.95610

H

1.27756

-2.17331

3.69007

H

1.43552

-1.41633

5.26409

H

3.55980

-2.45799

4.60610

H

3.73849

-0.72422

4.81768

H

3.51530

-2.17017

2.12781

H

4.98564

-1.49597

2.84807

H

-0.02621

0.45147

5.36096

H

-0.55990

1.26769

3.88964

H

-0.87958

-0.45931

4.11820

H

6.08496

4.59235

-0.18420

H

6.34527

2.30000

0.73155

H

2.37612

2.49696

2.34052

H

3.97348

5.84363

0.19779

H

2.13261

4.78764

1.48249

Table S11. Ib: ID No.5 (the lowest energy conformer)

Gibbs Free Energy

(298.15K, 1 atm)

-1286.915765 hartree

(22)

Total Energy

Atom

x

y

z

C

0.00000

0.00000

0.00000

C

0.00000

0.00000

1.39825

C

1.22593

0.00000

2.10428

C

2.42014

0.01341

1.35467

C

1.18785

0.02119

-0.72191

C

2.39652

0.04200

-0.04225

C

1.21869

-0.02204

3.63492

C

1.90662

1.19862

4.29467

C

3.43356

1.26490

4.20756

C

3.97148

1.30855

2.77831

C

1.70593

-1.36238

4.22168

C

4.76085

-0.76733

1.75843

C

4.54536

-2.05113

0.99641

C

-1.33964

-0.01329

2.10661

C

5.50635

-3.66163

-0.54070

C

5.58569

-2.45746

0.15105

C

3.44012

-2.89176

1.16284

C

4.40017

-4.49398

-0.37076

C

3.37434

-4.11043

0.49059

O

5.88937

-0.49933

2.15529

N

3.69260

0.07554

2.01575

H

-0.94787

-0.00695

-0.52743

H

1.17161

0.03511

-1.80567

H

3.33307

0.08041

-0.58478

H

0.17361

0.06477

3.93298

H

1.61808

1.20383

5.35227

H

1.48243

2.11062

3.85722

H

3.88933

0.41912

4.73178

H

3.77699

2.16764

4.72557

H

3.52682

2.14513

2.22931

H

5.05258

1.43554

2.78534

H

1.10595

-2.19352

3.84072

H

2.75120

-1.56727

3.98928

H

1.60380

-1.35320

5.31143

H

-1.48576

0.87655

2.72653

H

-1.45507

-0.88494

2.75757

H

-2.15083

-0.04009

1.37713

H

6.31278

-3.95661

-1.20274

H

6.45729

-1.82190

0.05554

H

2.63256

-2.60743

1.82243

H

4.34170

-5.43817

-0.90073

H

2.51824

-4.75889

0.63951

Table S12. Ic: ID No.6 (the lowest-energy conformer)

Gibbs Free Energy

(298.15K, 1 atm)

-866.581094 hartree

(23)

Total Energy

Atom

x

y

z

C

0.00000

0.00000

0.00000

C

0.00000

0.00000

1.39374

C

1.19559

0.00000

2.11733

C

2.40763

-0.02662

1.40498

C

1.20572

-0.00605

-0.69548

C

2.40540

-0.03448

0.00869

C

1.19800

0.05057

3.64264

C

1.70243

-1.24289

4.29860

C

3.22618

-1.40469

4.25396

C

3.83912

-1.41353

2.85168

C

4.74663

0.67449

1.93190

C

4.55664

2.01714

1.28264

C

3.41513

4.13183

0.97945

C

3.46938

2.85696

1.53688

C

5.59223

2.49102

0.46864

C

4.42990

4.59861

0.13870

C

5.52027

3.75414

-0.10525

O

5.86138

0.33805

2.31049

N

3.64248

-0.14397

2.12119

C

4.35029

5.96401

-0.49819

O

-0.10405

0.29580

4.17825

H

-0.94101

0.00074

-0.53840

H

-0.93894

-0.00823

1.93342

H

1.21573

-0.00826

-1.77935

H

3.35058

-0.06910

-0.51997

H

1.87202

0.86364

3.95081

H

1.20726

-2.09934

3.82829

H

1.37498

-1.21605

5.34131

H

3.49594

-2.34600

4.74462

H

3.69909

-0.60508

4.83502

H

3.40469

-2.21647

2.24797

H

4.91407

-1.57438

2.91510

H

2.57015

4.77467

1.20422

H

2.66649

2.52961

2.18479

H

6.45761

1.86041

0.30475

H

6.32995

4.09730

-0.74153

H

3.66931

6.62016

0.04795

H

5.33122

6.44455

-0.53318

H

3.98508

5.89392

-1.52870

H

-0.40223

1.16409

3.88711

Table S13. IIa: ID No.2 (the lowest-energy conformer)

Gibbs Free Energy

(298.15K, 1 atm)

-902.531377 hartree

(24)

Total Energy

Atom

x

y

z

C

0.00000

0.00000

0.00000

C

0.00000

0.00000

1.39894

C

1.22998

0.00000

2.08898

C

2.42258

0.01555

1.34510

C

1.18792

0.01184

-0.72286

C

2.40229

0.03175

-0.04988

C

1.26551

-0.04250

3.61668

C

1.85672

1.22218

4.27305

C

3.37876

1.37742

4.16961

C

3.93085

1.37294

2.74279

C

4.78316

-0.70451

1.74362

C

4.56830

-2.03525

1.07805

C

-1.33100

-0.01659

2.12147

C

5.50277

-3.74454

-0.36430

C

5.58850

-2.49490

0.23551

C

3.47981

-2.87574

1.33246

C

4.41355

-4.59047

-0.11943

C

3.41485

-4.13807

0.74764

O

5.91462

-0.36023

2.05895

N

3.68128

0.09732

2.03499

C

4.31893

-5.94212

-0.78279

O

1.88345

-1.24079

4.10696

H

-0.94778

-0.00704

-0.52755

H

1.16782

0.01856

-1.80666

H

3.33672

0.06274

-0.59668

H

0.24022

-0.12775

3.96969

H

1.36325

2.09583

3.83039

H

1.58012

1.20344

5.33194

H

3.87752

0.58911

4.74438

H

3.66857

2.32091

4.64455

H

3.47853

2.17688

2.15348

H

5.00935

1.52078

2.75549

H

-2.15109

-0.02341

1.40173

H

-1.44022

-0.90238

2.75406

H

-1.46480

0.86053

2.76163

H

6.30038

-4.07613

-1.02166

H

6.45247

-1.86299

0.06990

H

2.68567

-2.56794

2.00056

H

2.57146

-4.78219

0.97419

H

5.29666

-6.42734

-0.83874

H

3.64012

-6.60504

-0.24228

H

3.94270

-5.84897

-1.80754

H

2.82152

-1.20592

3.88744

Table S14. IIc: ID No.2 (the lowest-energy conformer)

Gibbs Free Energy

(298.15K, 1 atm)

-941.828118 hartree

(25)

Total Energy

Atom

x

y

z

C

0.00000

0.00000

0.00000

C

0.00000

0.00000

1.38958

C

1.19856

0.00000

2.11312

C

1.19512

-0.02009

3.62179

C

2.39740

0.00166

1.39364

C

2.40421

-0.02372

0.00179

C

1.20355

-0.03074

-0.71395

C

1.11851

0.06445

-2.21284

O

0.25468

0.76836

-2.72272

N

2.04174

-0.61745

-2.99068

C

2.00443

-0.40222

-4.44770

C

3.16567

0.46038

-4.93761

C

4.55032

-0.16239

-4.73485

C

4.94989

-0.44148

-3.25914

N

6.41153

-0.49466

-3.05867

C

2.84802

-1.70644

-2.52379

C

4.24990

-1.66615

-2.65561

C

4.97758

-2.74873

-2.15036

C

4.34942

-3.85089

-1.57456

C

2.96156

-3.89211

-1.48369

C

2.21749

-2.81897

-1.96015

C

7.00523

0.81109

-2.80749

C

7.16454

-1.23043

-4.07132

H

-0.93241

0.03950

-0.54993

H

-0.94567

0.01435

1.92229

H

2.10791

0.42050

4.02901

H

1.13028

-1.04709

3.99807

H

0.34152

0.52935

4.02603

H

3.34173

0.02337

1.92812

H

3.35282

-0.02441

-0.51899

H

1.05359

0.07790

-4.67330

H

2.02143

-1.38288

-4.93383

H

3.11611

1.43170

-4.43264

H

3.01864

0.65624

-6.00595

H

4.62511

-1.08868

-5.31516

H

5.29117

0.52756

-5.15166

H

4.60439

0.42068

-2.67645

H

6.05708

-2.70187

-2.17562

H

4.94737

-4.67124

-1.19349

H

2.46056

-4.74683

-1.04384

H

1.13625

-2.82665

-1.88977

H

6.95608

1.49731

-3.67347

H

8.06034

0.68423

-2.54984

H

6.51032

1.29295

-1.96106

H

8.17406

-1.42084

-3.69544

H

6.69603

-2.19417

-4.27640

H

7.26270

-0.69179

-5.02873

Table S15. IIIa (1): ID No. 27 (the lowest-energy conformer)

Gibbs Free Energy

(298.15K, 1 atm)

-961.215168 hartree

(26)

Total Energy

Atom

x

y

z

C

0.00000

0.00000

0.00000

C

0.00000

0.00000

1.38972

C

1.19869

0.00000

2.11315

C

1.19498

-0.02416

3.62175

C

2.39814

0.00765

1.39411

C

2.40490

-0.01125

0.00235

C

1.20402

-0.02195

-0.71291

C

1.12698

0.08061

-2.21004

O

0.24862

0.75663

-2.73372

N

2.08467

-0.54474

-2.98835

C

2.00899

-0.24280

-4.44242

C

3.11076

-0.90506

-5.26963

C

4.54424

-0.43742

-4.96234

C

4.87088

-0.40907

-3.44957

N

6.31367

-0.29441

-3.17591

C

2.87245

-1.66281

-2.56630

C

4.26036

-1.63959

-2.79184

C

5.00966

-2.77250

-2.46983

C

4.40852

-3.89133

-1.89648

C

3.03593

-3.89748

-1.65602

C

2.26785

-2.79173

-2.00784

C

7.00330

0.68217

-4.01574

C

6.56041

0.01607

-1.76775

H

-0.93206

0.03666

-0.55086

H

-0.94549

0.01091

1.92280

H

0.33919

0.52094

4.02717

H

1.13381

-1.05242

3.99520

H

2.10596

0.41876

4.03051

H

3.34180

0.03286

1.92973

H

3.35160

0.00129

-0.52227

H

1.03017

-0.56581

-4.81056

H

2.03563

0.84429

-4.55357

H

3.04365

-1.99111

-5.16524

H

2.89045

-0.68892

-6.31956

H

5.24832

-1.10971

-5.46364

H

4.69328

0.56219

-5.38020

H

4.34974

0.47167

-3.03010

H

6.07490

-2.75787

-2.66706

H

5.01000

-4.75721

-1.64318

H

2.55975

-4.76553

-1.21450

H

1.19500

-2.79854

-1.85657

H

6.96142

0.39937

-5.06680

H

6.59689

1.70560

-3.91188

H

8.05558

0.71135

-3.72460

H

6.17014

1.01065

-1.48320

H

6.09536

-0.72924

-1.12227

H

7.63572

0.00585

-1.57486

Table S16. IIIa (2): ID No.19

(the 2nd lowest-energy conformer)

Gibbs Free Energy

(298.15K, 1 atm)

-961.215024 hartree

(27)

6. Thermal ellipsoid plots (ORTEP drawing) of compounds Ib, Ic, IIc and IIIa.

(the ellipsoid contour: 50 % probability levels)

Ib Molecule I (chair)

Ib Molecule II (boat)

Ic

IIc

(28)

7.

1

H NMR spectra of Ia and IIa measured in CD

3

OD at 296K.

1

H NMR (CD

3

OD) of Ia

1

H NMR (CD

3

OD) of IIa

ab

u

n

d

a

n

ce

0

1

.0

2

.0

3

.0

4

.0

X : parts per Million : Proton

8.0

7.0

6.0

5.0

4.0

3.0

2.0

1.0

0

8

.8

7

4

.1

3

3

.6

1

2

.2

4

1

.4

9

1

.2

1

1

.1

5

1

.0

0

1

.0

0

0

.9

6

0

.2

5

0

.2

4

0

.2

3

0

.2

1

Author = y-soyaku Comment = single_pulse Creation_Time = 11-MAY-2015 14:54: Current_Time = 30-JAN-2016 15:30: Data_Format = 1D COMPLEX Dim_Size = 13107 Dim_Title = Proton Dim_Units = [ppm] Dimensions = X Filename = 42ZTY2-49-34_rt_Pr Machine = CWBFFBBXFX Revision_Time = 30-JAN-2016 15:30: Sample_Id = 42ZTY2-49-34 Site = JNM-ECA600 Spectrometer = DELTA2_NMR Probe_Recovery = 5[us] Scans = 16 Mod_Return = 1 Total_Scans = 16 X_Points = 16384 X_Prescans = 1 X_Domain = 1H X_Offset = 5[ppm] X_Freq = 600.1723046[MHz] X_Sweep = 11.26126126[kHz] X_Sweep_Clipped = 9.00900901[kHz] X_Resolution = 0.68733284[Hz] Irr_Domain = Proton Irr_Offset = 5[ppm] Irr_Freq = 600.1723046[MHz] Tri_Domain = Proton Tri_Offset = 5[ppm] Tri_Freq = 600.1723046[MHz] X_Acq_Duration = 1.4548992[s] Digital_Filter = TRUE Filter_Factor = 8 Af_Version = 1 X90 = 7.88[us] Delay_Of_Start = 1.99999974[s] Actual_Start_Time = 11-MAY-2015 14:54: Acq_Delay = 10.88[us] Digital_Filter_Status = 2P Clipped = FALSE Dc_Balanced = FALSE Af_Delay_Ratio = 0 Autoshim_Mode = AUTOSHIM OFF Buffer_Loop = 1 Buffer_Loop_Index = 1 Changer_Slot = 0 Changer_Slot_Position = 0 Collection_State = Collect End_Time = 11-MAY-2015 14:55: Experiment = proton.jxp Exp_Remaining = 1[s] PROCESSING PARAMETERS ----dc_balance( 0, FALSE ) sexp( 0.2[Hz], 0.0[s] ) trapezoid( 0[%], 0[%], 80[%], 100[%] ) zerofill( 1 ) fft( 1, TRUE, TRUE ) machinephase ppm

ab

u

n

d

a

n

ce

0

0

.1

0

.2

0

.3

0

.4

0

.5

0

.6

X : parts per Million : Proton

8.0

7.0

6.0

5.0

4.0

3.0

2.0

1.0

0

7

.6

3

2

5

7

.6

1

9

6

7

.3

2

8

4

7

.2

2

8

2

6

.9

7

8

0

6

.6

3

8

1

6

.6

2

5

2

6

.6

0

2

0

6

.5

8

9

2

5

.4

8

0

4

5

.4

7

7

7

5

.0

5

2

1

4

.9

4

6

6

4

.8

5

3

3

4

.8

2

6

4

4

.0

9

6

7

4

.0

8

4

8

3

.4

1

3

9

3

.4

1

1

1

3

.3

0

0

0

3

.2

9

7

3

2

.8

0

1

3

2

.7

9

7

8

2

.4

7

5

8

2

.2

2

9

1

2

.0

0

2

6

1

.6

4

2

7

1

.6

3

6

3

1

.6

2

1

1

1

.2

4

2

2

1

.2

3

0

2

1

.2

1

8

3

5

.3

0

3

.9

4

2

.0

2

1

.3

1

1

.0

9

1

.0

4

1

.0

3

1

.0

1

1

.0

0

0

.9

8

0

.9

5

0

.9

4

0

.6

9

0

.5

9

0

.5

9

0

.3

4

0

.3

2

0

.3

1

0

.1

6

4

3

.3

9

m

Filename = 42JHTA12-157-30_Proton-1-6 Author = y-soyaku Experiment = proton.jxp Sample_Id = 42JHTA12-157-30 Solvent = METHANOL-D4 Creation_Time = 11-MAY-2015 20:12:03 Revision_Time = 30-JAN-2016 14:16:49 Current_Time = 30-JAN-2016 14:40:30 Comment = single_pulse Data_Format = 1D COMPLEX Dim_Size = 209715 Dim_Title = Proton Dim_Units = [ppm] Dimensions = X Site = JNM-ECA600 Spectrometer = DELTA2_NMR Field_Strength = 14.09636928[T] (600[MHz]) X_Acq_Duration = 1.4548992[s] X_Domain = 1H X_Freq = 600.1723046[MHz] X_Offset = 5[ppm] X_Points = 16384 X_Prescans = 1 X_Resolution = 0.68733284[Hz] X_Sweep = 11.26126126[kHz] X_Sweep_Clipped = 9.00900901[kHz] Irr_Domain = Proton Irr_Freq = 600.1723046[MHz] Irr_Offset = 5[ppm] Tri_Domain = Proton Tri_Freq = 600.1723046[MHz] Tri_Offset = 5[ppm] Clipped = FALSE Scans = 8 Total_Scans = 8 Relaxation_Delay = 5[s] Recvr_Gain = 42 Temp_Get = 22.7[dC] X_90_Width = 7.88[us] X_Acq_Time = 1.4548992[s] X_Angle = 45[deg] X_Atn = 2.5[dB] X_Pulse = 3.94[us] Irr_Mode = Off Tri_Mode = Off Dante_Presat = FALSE Initial_Wait = 1[s] Repetition_Time = 6.4548992[s] PROCESSING PARAMETERS ----dc_balance( 0, FALSE ) sexp( 0.2[Hz], 0.0[s] ) trapezoid( 0[%], 0[%], 80[%], 100[%] ) zerofill( 16 ) fft( 1, TRUE, TRUE ) machinephase ppm 以 以 以 以以以以以 にににに由由由由由由由由 ::::: 42JHTA12-157-30_Proton-1-1.jdf

IIa

anti : syn

1 : 0.3

anti : syn

1 : 0.24

Ia

anti : syn

1 : 0.3

Figure S1.  1 H NMR spectra (600 MHz in DMSO-d
Figure S2.  1 H NMR spectra (600 MHz in DMSO-d
Figure S3. VT-NMR of Ia.
Figure S6. VT NMR of Ib.
+7

参照

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