Supporting Information

N-Heterocyclic Carbene-Catalyzed [3+2] Annulation of Bromoenals with

3-Aminooxindoles: Highly Enantioselective Synthesis of Spirocyclic

Oxindolo-γ-Lactams

Kun-Quan Chen,a,b Yao Li,a,b Chun-Lin Zhang,a De-Qun Sun*b and Song Ye*a

a Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular

Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing

100190, China. E-mail: songye@iccas.ac.cn

b Marine College, Shandong University at Weihai, 180 Wenhua West Road, Weihai 264209,

China.. E-mail: dequn.sun@sdu.edu.cn.

Table of Contents

Part I NMR Spectra ................................................................................................. 1 

Part II HPLC Spectra ............................................................................................ 20 

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2016

 

1  

Part I NMR Spectra

3a

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.0919

2.7793

2.7942

2.8120

2.8270

3.6717

3.6998

3.7037

3.7324

3.8145

3.8295

3.8424

3.8574

4.0881

4.1199

5.0044

5.0362

6.3841

6.3978

6.4115

6.9228

6.9380

7.0638

7.0785

7.0938

7.1359

7.1507

7.1607

7.1647

7.1756

7.1911

7.1951

7.2887

7.3035

7.3182

7.4208

7.4349

8.99

1.00

1.02

1.01

1.01

1.00

2.97

2.12

2.17

5.10

1.01

1.02

NAME n-3+2-1EXPNO 9PROCNO 1Date_ 20150428Time 8.24INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 31.72DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300121 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-290

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

27.55

35.15

44.08

49.01

71.72

83.86

109.66

122.16

123.26

126.64

127.35

128.52

128.61

128.72

128.75

129.89

132.67

134.75

143.49

148.08

173.56

174.04

NAME n-3+2-1EXPNO 10PROCNO 1Date_ 20150428Time 8.26INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 88DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577763 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-290

 

2  

NH

O

N

O

Ph

Boc

3b

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

1.1516

2.7331

2.7517

2.7740

2.7926

3.5544

3.5893

3.6301

3.7163

3.7350

3.7510

3.7695

6.6454

6.6646

6.8612

6.8801

7.1306

7.1487

7.1673

7.1785

7.1838

7.2064

7.2246

7.2428

7.2621

7.2781

7.2974

7.3803

7.3987

8.63

1.00

1.05

1.03

1.09

1.94

6.65

1.02

NAME n-3+2-2EXPNO 59PROCNO 1Date_ 20150508Time 8.03INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 32768SOLVENT CDCl3NS 16DS 0SWH 8012.820 HzFIDRES 0.244532 HzAQ 2.0447731 secRG 206.33DW 62.400 usecDE 6.50 usecTE 298.8 KD1 2.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 400.2424716 MHzNUC1 1HP1 14.80 usecSI 65536SF 400.2400088 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-311

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

27.54

34.91

49.15

72.02

84.22

110.11

122.54

123.32

128.23

128.42

128.47

129.05

129.88

132.53

140.98

148.20

173.51

175.31

NAME n-3+2-2EXPNO 60PROCNO 1Date_ 20150508Time 8.08INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 263DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 206.33DW 20.800 usecDE 6.50 usecTE 299.9 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 100.6504916 MHzNUC1 13CP1 10.00 usecSI 32768SF 100.6404141 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-311

 

3  

3c

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.0906

2.7151

2.7389

2.7532

2.7711

2.7853

3.5924

3.6203

3.6522

3.6917

3.7059

3.7194

3.7336

6.5872

6.6027

6.8120

6.8270

7.1068

7.1214

7.1366

7.1623

7.1710

7.1770

7.1851

7.1916

7.2666

7.3161

7.3313

7.3465

7.3856

7.4002

9.16

4.17

2.12

1.00

1.99

4.34

1.11

1.11

NAME n-3+2-1EXPNO 7PROCNO 1Date_ 20150428Time 8.06INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 31.72DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300107 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-305

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

25.69

27.50

34.84

49.19

72.06

83.76

108.24

121.97

123.20

128.04

128.11

128.19

128.35

128.65

129.85

132.47

143.83

148.05

173.69

NAME n-3+2-1EXPNO 8PROCNO 1Date_ 20150428Time 8.10INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 245DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577734 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-305

 

4  

3d

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.5436

0.5622

0.5807

0.8564

0.8741

0.8921

0.9114

0.9266

1.0067

1.0259

1.0455

1.0644

1.0814

2.7279

2.7451

2.7673

2.7845

2.8874

2.9038

2.9090

2.9228

2.9385

2.9437

2.9600

3.4842

3.4986

3.5066

3.5201

3.5333

3.5413

3.5557

3.6086

3.6434

3.6827

3.7163

3.7335

3.7511

3.7682

6.6095

6.6290

6.8228

6.8411

7.1040

7.1217

7.1412

7.1646

7.1688

7.1831

7.1869

7.2673

7.2988

7.3014

7.3182

7.3207

7.3375

7.3401

7.3888

7.4072

2.99

11.5

3

1.00

1.00

1.01

2.02

1.02

1.98

4.06

1.02

0.98

NAME n-3+2-2EXPNO 55PROCNO 1Date_ 20150428Time 8.10INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 32768SOLVENT CDCl3NS 16DS 0SWH 8012.820 HzFIDRES 0.244532 HzAQ 2.0447731 secRG 140.59DW 62.400 usecDE 6.50 usecTE 298.0 KD1 2.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 400.2424716 MHzNUC1 1HP1 14.80 usecSI 65536SF 400.2400067 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-307

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

11.35

20.55

27.50

34.79

41.63

49.02

71.71

83.76

108.49

122.14

122.95

128.24

128.34

128.36

128.75

129.78

132.53

143.77

148.05

173.51

173.75

NAME n-3+2-2EXPNO 57PROCNO 1Date_ 20150428Time 8.16INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 102DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 206.33DW 20.800 usecDE 6.50 usecTE 298.3 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 100.6504916 MHzNUC1 13CP1 10.00 usecSI 32768SF 100.6404158 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-307

 

5  

3e

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.1619

2.7874

2.8019

2.8198

2.8343

3.6589

3.6872

3.7192

3.7694

3.7839

3.7971

3.8116

4.0930

4.1249

4.9745

5.0064

6.3014

6.3092

6.3184

6.3262

6.3760

6.3910

6.8759

6.8795

6.8935

6.8968

6.9110

6.9513

6.9666

7.0720

7.0871

7.1020

7.1459

7.1605

7.1755

7.1885

7.2034

7.2184

7.2624

7.3120

7.3267

7.3413

9.08

1.00

1.02

1.02

1.02

1.01

1.03

2.05

3.27

2.28

4.14

1.10

NAME n-3+2-1EXPNO 20PROCNO 1Date_ 20150512Time 21.35INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 31.72DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300109 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-314

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

27.68

35.16

44.25

49.05

71.86

84.21

110.22

110.41

110.47

116.02

116.21

126.63

127.50

128.61

128.70

128.80

128.86

130.25

130.31

132.38

134.46

139.38

139.39

148.08

158.56

160.49

173.15

173.88

NAME n-3+2-1EXPNO 21PROCNO 1Date_ 20150512Time 21.39INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 172DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577740 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-314

 

6  

3f

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.1633

2.7873

2.8022

2.8201

2.8350

3.6476

3.6755

3.6801

3.7082

3.7811

3.7960

3.8089

3.8238

4.0917

4.1236

4.9623

4.9941

6.3031

6.3198

6.3721

6.3871

6.9579

6.9730

7.0714

7.0861

7.1014

7.1465

7.1518

7.1561

7.1608

7.1685

7.1727

7.1925

7.2078

7.2233

7.2620

7.3121

7.3269

7.3417

7.4287

7.4326

9.02

1.00

1.05

1.09

1.14

0.99

1.00

2.12

1.90

2.25

2.17

2.11

1.22

1.16

NAME n-3+2-1EXPNO 22PROCNO 1Date_ 20150528Time 7.50INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 31.72DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300110 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-319

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

27.69

35.15

44.21

48.98

71.64

84.29

110.72

122.63

126.63

127.55

128.63

128.72

128.74

128.83

128.89

129.75

130.41

132.33

134.32

141.99

148.06

173.06

173.71NAME n-3+2-1

EXPNO 23PROCNO 1Date_ 20150528Time 7.54INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 78DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577733 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-319

 

7  

3g

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.0217

2.2961

2.6933

2.7082

2.7260

2.7409

3.5906

3.6189

3.6513

3.7301

3.7450

3.7580

3.7729

3.9809

4.0127

4.9116

4.9433

6.2027

6.2186

6.2958

6.3108

6.8651

6.8805

6.9052

6.9210

6.9816

6.9966

7.0116

7.0528

7.0674

7.0822

7.0933

7.1085

7.1237

7.1823

7.1910

7.2152

7.2299

7.2446

8.93

3.00

0.99

0.99

1.00

1.04

1.00

0.98

2.01

3.07

2.02

3.06

1.26

1.05

NAME n-3+2-1EXPNO 12PROCNO 1Date_ 20150508Time 7.57INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 31.72DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300465 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-312

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

21.23

27.54

35.17

44.06

48.98

71.80

83.77

109.42

122.82

126.63

127.27

128.46

128.54

128.63

128.66

128.71

130.07

132.79

132.93

134.88

141.10

148.13

173.58

173.98

NAME n-3+2-1EXPNO 13PROCNO 1Date_ 20150508Time 8.02INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 123DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577769 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-312

 

8  

3h

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.1264

2.7680

2.7827

2.8004

2.8151

3.6666

3.6949

3.7270

3.7872

3.8067

3.8293

4.0574

4.0891

4.9745

5.0063

6.2901

6.3071

6.3744

6.3893

6.7041

6.7085

6.7210

6.7254

6.9487

6.9638

7.0453

7.0496

7.0615

7.0764

7.0915

7.1325

7.1469

7.1620

7.1729

7.1881

7.2033

7.2972

7.3118

7.3264

9.28

0.99

5.19

1.04

1.00

1.03

2.01

1.04

2.15

3.11

3.10

1.06

NAME n-3+2-1EXPNO 28PROCNO 1Date_ 20150528Time 16.42INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 31.72DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300071 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-ly-28

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

27.59

35.15

44.13

49.06

56.03

72.02

83.87

109.06

110.24

114.35

126.63

127.29

128.48

128.60

128.66

128.71

129.75

132.65

134.82

136.77

148.09

156.55

173.53

173.77

NAME n-3+2-1EXPNO 29PROCNO 1Date_ 20150528Time 19.47INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 59DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577797 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-ly-51

 

9  

3i

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.0935

2.7821

2.7970

2.8148

2.8297

3.6741

3.7023

3.7348

3.8127

3.8276

3.8406

3.8555

4.0870

4.1188

5.0044

5.0362

6.3829

6.3959

6.4086

6.9229

6.9382

7.0634

7.0782

7.0933

7.1350

7.1497

7.1628

7.1773

7.1932

7.2095

7.2614

7.2887

7.3035

7.3182

7.4187

7.4331

9.05

0.99

1.00

1.01

1.06

1.00

2.97

2.04

2.13

5.04

1.04

1.10

NAME n-3+2-1EXPNO 18PROCNO 1Date_ 20150511Time 19.28INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 31.72DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300116 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-316

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

27.58

35.18

44.11

49.04

71.74

83.89

109.68

122.18

123.28

126.66

127.37

128.54

128.57

128.64

128.74

128.77

129.90

132.70

134.79

143.52

148.11

173.57

174.06

NAME n-3+2-1EXPNO 19PROCNO 1Date_ 20150511Time 19.30INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 151DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577723 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-316

 

10  

3j

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.0997

2.7745

2.7897

2.8074

2.8225

3.6044

3.6326

3.6652

3.7813

3.7964

3.8091

3.8243

4.1095

4.1411

5.0113

5.0429

6.4700

6.4840

6.8183

6.8356

6.8527

6.8608

6.8717

6.8890

7.1229

7.1374

7.1526

7.1582

7.1748

7.1925

7.2094

7.2255

7.2408

7.2616

7.4099

7.4244

9.77

1.03

1.07

1.05

1.06

1.00

3.01

4.29

6.89

1.13

NAME n-3+2-1EXPNO 61PROCNO 1Date_ 20151030Time 16.40INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 62.06DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300113 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-401

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

27.58

35.26

44.12

48.26

71.59

84.00

109.65

115.63

115.80

122.20

123.40

126.73

127.65

128.37

128.47

128.70

130.06

130.22

130.28

134.75

143.53

148.05

173.23

173.94

NAME n-3+2-1EXPNO 62PROCNO 1Date_ 20151030Time 16.44INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 114DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577716 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-401

 

11  

3k

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.1042

2.7698

2.7849

2.8026

2.8177

3.6028

3.6308

3.6349

3.6635

3.7702

3.7853

3.7980

3.8131

4.0952

4.1268

5.0560

5.0876

6.4634

6.4778

6.8351

6.8519

7.1223

7.1392

7.1568

7.1719

7.1861

7.1995

7.2213

7.2365

7.2617

7.4066

7.4212

8.02

0.88

0.89

0.88

0.90

1.00

2.64

1.81

7.38

0.93

NAME n-3+2-1EXPNO 14PROCNO 1Date_ 20150508Time 8.09INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 31.72DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300114 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-310

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

27.59

35.14

44.22

48.35

71.48

84.04

109.74

122.19

123.42

126.67

127.67

128.26

128.80

128.97

129.96

130.10

131.32

134.61

134.67

143.54

148.01

173.11

173.89

NAME n-3+2-1EXPNO 15PROCNO 1Date_ 20150508Time 8.14INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 98DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577723 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-310

 

12  

NO

N

O

Boc

Bn

CN

3l

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.1101

2.7937

2.8089

2.8265

2.8418

3.6144

3.6420

3.6471

3.6748

3.8183

3.8335

3.8459

3.8611

4.1320

4.1632

4.9290

4.9602

6.5498

6.5647

6.5748

6.5905

6.9698

6.9864

7.1674

7.1822

7.1925

7.1976

7.2070

7.2467

7.2620

7.2663

7.2804

7.2821

7.2977

7.3648

7.3813

7.4348

7.4493

9.20

1.02

1.00

1.00

1.01

1.00

2.98

2.05

3.10

2.34

2.03

1.02

NAME n-3+2-1EXPNO 45PROCNO 1Date_ 20150602Time 8.20INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 55.37DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300088 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-323

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

27.56

34.73

44.21

48.72

71.19

84.27

109.66

112.60

118.40

122.26

123.62

126.97

127.88

128.04

128.81

129.30

130.37

132.25

134.70

138.15

143.43

147.87

172.54

173.59

NAME n-3+2-1EXPNO 46PROCNO 1Date_ 20150602Time 8.23INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 84DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577743 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-323

 

13  

3m

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.0921

2.3282

2.7468

2.7650

2.7873

2.8056

3.6287

3.6642

3.7042

3.7729

3.7911

3.8075

3.8259

4.0775

4.1173

5.0553

5.0950

6.3938

6.4127

6.4292

6.4479

6.8056

6.8253

6.9676

6.9869

7.0533

7.0719

7.0905

7.1225

7.1420

7.1605

7.1709

7.1906

7.2092

7.2632

7.4057

7.4232

9.76

3.23

1.03

1.00

1.07

1.06

1.00

3.15

2.26

2.12

2.08

3.76

1.12

NAME n-3+2-2EXPNO 70PROCNO 1Date_ 20150528Time 8.04INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 32768SOLVENT CDCl3NS 16DS 0SWH 8012.820 HzFIDRES 0.244532 HzAQ 2.0447731 secRG 102.73DW 62.400 usecDE 6.50 usecTE 298.7 KD1 2.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 400.2424716 MHzNUC1 1HP1 14.80 usecSI 65536SF 400.2400087 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-318

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

21.36

27.55

35.34

44.10

48.69

71.74

83.79

109.63

122.15

123.21

126.75

127.33

128.50

128.53

128.66

129.42

129.65

129.81

134.81

138.18

143.51

148.10

173.67

174.13

2.31

7.19

2.99

2.08

2.10

48.6

8

1.70

2.51

1.84

2.29

3.92

2.69

10.5

39.

17

NAME n-3+2-2EXPNO 69PROCNO 1Date_ 20150514Time 16.49INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 65DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 206.33DW 20.800 usecDE 6.50 usecTE 298.1 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 100.6504916 MHzNUC1 13CP1 10.00 usecSI 32768SF 100.6404178 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-318

 

14  

3n

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.0939

2.7485

2.7670

2.7892

2.8078

3.6074

3.6426

3.6473

3.6833

3.7550

3.7673

3.7867

3.8034

3.8217

4.0766

4.1164

5.0762

5.1160

6.4054

6.4187

6.4234

6.4343

6.6813

6.7030

6.8258

6.8474

7.0720

7.0899

7.1089

7.1272

7.1446

7.1621

7.1807

7.1835

7.2002

7.2027

7.2192

7.2216

7.4042

7.4217

9.01

1.00

5.13

1.07

1.00

3.05

2.06

2.03

5.07

1.02

NAME n-3+2-2EXPNO 61PROCNO 1Date_ 20150510Time 20.48INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zg30TD 32768SOLVENT CDCl3NS 16DS 0SWH 8012.820 HzFIDRES 0.244532 HzAQ 2.0447731 secRG 102.73DW 62.400 usecDE 6.50 usecTE 298.0 KD1 2.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 400.2424716 MHzNUC1 1HP1 14.80 usecSI 65536SF 400.2400069 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-313

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

27.54

35.35

44.02

48.32

55.20

71.75

83.79

109.59

114.07

122.14

123.23

124.48

126.65

127.42

128.54

128.65

129.66

129.84

134.74

143.52

148.09

159.81

173.64

174.13

NAME n-3+2-2EXPNO 62PROCNO 1Date_ 20150510Time 20.51INSTRUM spectPROBHD 5 mm PABBO BB/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 114DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 206.33DW 20.800 usecDE 6.50 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 100.6504916 MHzNUC1 13CP1 10.00 usecSI 32768SF 100.6404181 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-313

 

15  

3o

-0.59.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

1.0990

2.7732

2.7882

2.8059

2.8209

3.6116

3.6394

3.6442

3.6721

3.7616

3.7766

3.7894

3.8044

4.1275

4.1591

4.9923

5.0238

6.4946

6.5101

6.5291

6.5437

6.7998

6.8156

6.8433

7.0462

7.0620

7.0777

7.1247

7.1387

7.1543

7.1728

7.1882

7.1939

7.2032

7.2261

7.2277

7.2417

7.2435

7.4079

7.4223

9.38

1.03

1.07

1.01

1.01

1.00

2.97

1.94

1.23

4.18

1.87

0.84

NAME n-3+2-1EXPNO 39PROCNO 1Date_ 20150530Time 20.05INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 31.72DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300111 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-320

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

27.56

34.92

44.17

48.53

71.41

84.06

109.73

122.14

123.48

126.61

126.76

127.59

128.18

128.67

128.79

129.92

130.15

134.56

134.82

134.85

143.47

147.98

173.02

173.77

NAME n-3+2-1EXPNO 36PROCNO 1Date_ 20150529Time 21.40INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 50DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577741 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-320

 

16  

3p

-0.59.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

1.1013

2.8676

2.8841

2.9014

2.9179

3.3802

3.4073

3.4139

3.4410

3.4766

3.5982

4.1814

4.2133

4.5293

4.5458

4.5562

4.5727

5.1295

5.1614

6.4499

6.4654

6.5755

6.5904

6.6619

6.6677

6.6795

6.6854

7.0934

7.1118

7.1273

7.1577

7.1641

7.1823

7.1977

7.2625

7.2666

7.2844

7.4707

7.4853

9.41

1.05

1.23

3.14

1.09

1.05

1.00

1.20

2.09

1.13

6.59

1.76

1.12

NAME n-3+2-1EXPNO 42PROCNO 1Date_ 20150602Time 8.12INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 31.72DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300108 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-322

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

27.57

37.68

44.10

45.59

55.55

71.82

83.99

109.39

114.98

116.38

116.74

123.07

124.20

126.48

127.48

127.61

128.80

129.95

133.69

133.89

135.02

143.20

147.95

159.14

172.94

174.66

NAME n-3+2-1EXPNO 43PROCNO 1Date_ 20150602Time 8.16INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 83DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577724 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-322

 

17  

3q

-0.59.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

1.0933

2.8398

2.8561

2.8734

2.8898

3.4738

3.5011

3.5073

3.5346

4.1393

4.1711

4.5668

4.5832

4.5939

4.6102

5.0751

5.1068

6.4084

6.4240

6.4928

6.5079

7.0698

7.0848

7.0922

7.0998

7.1071

7.1506

7.1672

7.1840

7.2033

7.4461

7.4608

7.6137

7.6185

7.6306

9.11

1.00

1.02

1.00

0.98

1.02

1.02

1.97

3.07

4.99

1.02

1.03

NAME n-3+2-1EXPNO 64PROCNO 1Date_ 20151110Time 18.44INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 55.37DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300111 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-403

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

27.57

37.06

42.93

44.11

71.74

84.00

109.53

123.16

123.75

126.68

127.44

127.46

127.88

128.77

129.44

129.88

129.90

130.05

131.28

134.91

135.55

143.04

147.96

173.06

174.40

NAME n-3+2-1EXPNO 65PROCNO 1Date_ 20151110Time 18.47INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 68DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577715 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-403

 

18  

3r

-0.59.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

1.0942

1.6406

2.8099

2.8260

2.8438

2.8599

3.5458

3.5732

3.5795

3.6070

4.0577

4.0896

4.1762

4.1924

4.2033

4.2195

5.1233

5.1551

6.3479

6.3634

6.3786

7.0038

7.0181

7.0576

7.0727

7.0878

7.1027

7.1333

7.1480

7.1623

7.1778

7.1931

7.2616

7.4144

7.4290

7.5711

7.5862

9.24

2.94

1.00

0.97

1.01

0.97

1.00

2.94

1.11

3.12

4.08

1.00

1.00

NAME n-3+2-1EXPNO 16PROCNO 1Date_ 20150510Time 20.44INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 31.72DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300115 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-315

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

19.62

27.57

37.58

43.57

44.13

72.13

83.88

109.82

122.66

123.03

126.58

126.80

127.34

128.11

128.46

128.78

129.10

129.88

130.82

131.60

134.78

138.01

143.27

148.03

173.64

174.59

NAME n-3+2-1EXPNO 17PROCNO 1Date_ 20150510Time 20.47INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 124DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577724 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-315

 

19  

3s

-0.59.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

1.0836

2.7069

2.7229

2.7401

2.7562

3.1037

3.4957

3.5237

3.5287

3.5568

4.0891

4.1205

4.4341

4.4501

4.4619

4.4780

5.0952

5.1265

6.4466

6.4575

6.4601

6.4749

6.6133

6.6272

7.0793

7.0941

7.1005

7.1069

7.1090

7.1144

7.1175

7.1297

7.1324

7.1452

7.1479

7.1526

7.1656

7.1807

7.1853

7.1990

7.2645

7.3122

7.3169

7.3297

7.3344

7.3850

7.3870

7.4011

7.5406

7.5451

9.90

1.07

3.24

1.16

1.01

1.07

1.98

2.09

5.41

1.07

1.10

1.00

NAME n-3+2-1EXPNO 37PROCNO 1Date_ 20150530Time 19.57INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 10000.000 HzFIDRES 0.152588 HzAQ 3.2768500 secRG 31.72DW 50.000 usecDE 6.50 usecTE 298.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========SFO1 500.1330885 MHzNUC1 1HP1 10.60 usecSI 65536SF 500.1300098 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

ckq-321r

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

27.55

35.69

39.73

44.26

55.15

71.37

83.83

109.12

112.35

113.29

122.68

123.12

124.18

126.90

127.54

128.80

128.98

129.31

131.79

132.11

135.22

143.13

148.04

157.23

173.40

174.24

NAME n-3+2-1EXPNO 38PROCNO 1Date_ 20150530Time 20.01INSTRUM spectPROBHD 5 mm CPPBBO BBPULPROG zgpg30TD 65536SOLVENT CDCl3NS 73DS 4SWH 29761.904 HzFIDRES 0.454131 HzAQ 1.1010548 secRG 192.89DW 16.800 usecDE 18.00 usecTE 298.0 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========SFO1 125.7703637 MHzNUC1 13CP1 9.80 usecSI 32768SF 125.7577733 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

ckq-321r

 

Part II

I HPLC SSpectra

 

20 

 

 

21 

 

 

22 

 

 

23 

 

 

24 

 

 

25 

 

 

26 

 

 

27 

 

 

28 

 

 

29 

 

 

30 

 

 

31 

 

 

32 

 

 

33 

 

 

34 

 

 

35 

 

 

36 

N

O

Boc

NO

O

Bn

Cl

3q

 

 

37 

 

 

38