the royal society of chemistry · s2 data: s. no. details page no. 1. copies of 1h nmr spectra of...

S1

SUPPORTING INFORMATION

Chiral bicyclic skeleton-tethered bipyridine–Zn(OTf)2 complex as Lewis acid: Enantioselective Friedel–Crafts alkylation of indoles with nitroalkenes

Kesa Venkatanna, Santhakumar Yeswanth Kumar, Muthupandi Karthick, Ramanathan

Padmanaban, Chinnasamy Ramaraj Ramanathan*

Department of Chemistry, Pondicherry University, Puducherry – 605 014, India.

E-mail: [email protected]

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2019

S2

Data:

S. No. Details Page No.

1. Copies of 1H NMR spectra of compounds, 2a-2q S4 – S12

2. Copies of 1H, 13C NMR spectra of compounds, 3a-3s S14 – S32

3. HPLC chromatogram of compounds, 3a-3s S34 – S72

4. Comparison of observed and reported optical rotations for 3a-3s S73 – S74

5. Cartesian Coordinates for CRCB tethered bipyridine-Zn--nitrostyrene

complex I

S75 – S77

S3

1. Copies of 1H NMR spectra of

compounds, 2a-2q

S4

11 10 9 8 7 6 5 4 3 2 1 0 ppm

7.260

7.436

7.453

7.457

7.468

7.471

7.484

7.487

7.491

7.505

7.540

7.544

7.549

7.561

7.571

7.605

7.992

8.027

2.00

0.90

1.99

1.12

1.00

Current Data ParametersNAME KV-IV-685EXPNO 1PROCNO 1

F2 - Acquisition ParametersDate_ 20160708Time 15.52INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 228DW 60.800 usecDE 6.00 usecTE 298.8 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 11.42 usecPL1 -3.00 dBSFO1 400.1324710 MHz

F2 - Processing parametersSI 32768SF 400.1300050 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

11 10 9 8 7 6 5 4 3 2 1 ppm

1.576

3.955

6.969

6.991

7.003

7.006

7.022

7.024

7.041

7.043

7.260

7.443

7.447

7.462

7.466

7.479

7.484

7.867

7.901

8.127

8.161

3.01

1.04

1.08

2.13

1.00

1.02

Current Data ParametersNAME KV-V-763EXPNO 1PROCNO 1




S5

10 9 8 7 6 5 4 3 2 1 0 ppm

3.848

7.032

7.047

7.129

7.148

7.260

7.343

7.364

7.384

7.549

7.583

7.948

7.982

2.94

2.05

1.06

1.05

1.02

1.00

Current Data ParametersNAME MK-3-OME-NSEXPNO 1PROCNO 1

F2 - Acquisition ParametersDate_ 20190122Time 14.20INSTRUM spectPROBHD 5 mm BBO BB-1HPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 287DW 60.800 usecDE 6.00 usecTE 295.7 KD1 1.00000000 secTD0 1



11 10 9 8 7 6 5 4 3 2 1 ppm

1.594

3.866

6.942

6.965

7.260

7.490

7.498

7.512

7.532

7.954

7.988

3.00

1.97

3.01

0.98

Current Data ParametersNAME KV-IV-684EXPNO 1PROCNO 1




S6

1234567891011 ppm

1.575

7.260

7.320

7.324

7.339

7.343

7.358

7.363

7.365

7.370

7.385

7.388

7.404

7.407

7.521

7.555

7.564

7.569

7.583

7.587

7.673

7.681

7.684

7.700

7.704

8.384

8.418

2.26

1.08

1.04

0.95

1.00





9 8 7 6 5 4 3 2 1 ppm

7.260

7.317

7.337

7.356

7.468

7.487

7.541

7.576

7.611

7.616

7.618

7.631

7.636

7.693

7.697

7.702

7.911

1.06

1.03

1.04

0.95

1.02

1.00

Current Data ParametersNAME KV-VI-991EXPNO 1PROCNO 1




S7

11 10 9 8 7 6 5 4 3 2 1 ppm

1.572

7.260

7.406

7.427

7.559

7.590

7.593

7.611

7.931

7.965

2.05

1.96

0.80

1.00





11 10 9 8 7 6 5 4 3 2 1 0 ppm

2.409

7.246

7.260

7.266

7.434

7.454

7.549

7.583

7.967

8.001

3.00

2.03

1.96

0.95

0.94





S8

9 8 7 6 5 4 3 2 1 0 ppm

1.635

7.260

7.392

7.411

7.422

7.441

7.449

7.454

7.472

7.524

7.542

7.577

7.909

7.943

3.31

1.02

1.11

1.00

Current Data ParametersNAME MK-3L-NSEXPNO 1PROCNO 1

F2 - Acquisition ParametersDate_ 20190122Time 14.32INSTRUM spectPROBHD 5 mm BBO BB-1HPULPROG zg30TD 65536SOLVENT CDCl3NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 287DW 60.800 usecDE 6.00 usecTE 295.6 KD1 1.00000000 secTD0 1



11 10 9 8 7 6 5 4 3 2 1 ppm

1.583

7.260

7.424

7.440

7.446

7.450

7.481

7.487

7.503

7.545

7.579

7.947

7.981

1.97

2.06

1.05

1.00





S9

11 10 9 8 7 6 5 4 3 2 1 ppm

7.123

7.131

7.136

7.148

7.152

7.156

7.160

7.168

7.173

7.181

7.260

7.517

7.537

7.544

7.551

7.557

7.562

7.566

7.574

7.579

7.587

7.964

7.998

2.09

3.18

1.00





9 8 7 6 5 4 3 2 1 ppm

7.260

7.656

7.666

7.686

7.690

7.706

7.865

7.884

8.038

8.072

8.339

8.342

8.345

8.347

8.360

8.362

8.365

8.368

2.27

1.03

1.05

1.11

1.00

Current Data ParametersNAME KV-VI-973-aEXPNO 1PROCNO 1




S10

11 10 9 8 7 6 5 4 3 2 1 0 ppm

2.409

7.246

7.260

7.266

7.434

7.454

7.549

7.583

7.967

8.001

3.00

2.03

1.96

0.95

0.94





123456789 ppm

1.601

7.260

7.506

7.525

7.545

7.574

7.577

7.592

7.594

7.598

7.602

7.612

7.615

7.622

7.632

7.635

7.642

7.649

7.653

7.656

7.660

7.670

7.676

7.700

7.752

7.769

7.913

7.916

7.933

7.935

7.936

7.990

7.993

7.999

8.007

8.011

8.020

8.128

8.129

8.149

8.828

8.861

1.06

1.06

2.21

0.99

1.37

1.12

1.06

1.00





S11

11 10 9 8 7 6 5 4 3 2 1 ppm

1.588

7.260

7.546

7.550

7.564

7.567

7.579

7.582

7.584

7.587

7.598

7.603

7.608

7.616

7.619

7.685

7.719

7.859

7.878

7.888

7.893

7.899

7.910

8.021

8.149

8.183

3.07

0.97

3.09

1.00

0.95





11 10 9 8 7 6 5 4 3 2 1 ppm

1.591

6.569

6.573

6.578

6.582

6.887

6.896

7.260

7.506

7.539

7.589

7.593

7.758

7.791

1.02

0.99

0.98

0.97

1.00





S12

11 10 9 8 7 6 5 4 3 2 1 ppm

1.590

7.138

7.147

7.150

7.160

7.260

7.451

7.463

7.497

7.558

7.571

8.137

8.170

1.00

2.00

1.03

1.00





S13

2. Copies of 1H, 13C NMR spectra of

compounds, 3a-3s

S14

11 10 9 8 7 6 5 4 3 2 1 ppm

0.000

4.838

4.859

4.870

4.891

4.964

4.983

4.995

5.014

5.094

5.114

5.134

6.943

6.947

6.979

6.981

6.999

7.016

7.019

7.099

7.102

7.120

7.122

7.137

7.140

7.174

7.179

7.185

7.192

7.198

7.220

7.234

7.240

7.250

7.256

7.265

7.285

7.358

7.378

1.01

1.03

1.00

1.00

1.03

1.01

1.19

5.12

1.02

0.81


F2 - Acquisition ParametersDate_ 20161024Time 10.50INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zg30TD 65536SOLVENT CDCl3

NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 144DW 60.800 usecDE 6.00 usecTE 292.6 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========NUC1 1H

P1 11.42 usecPL1 -3.00 dBSFO1 400.1324710 MHz


PROTON CDCl3 {D:\CRR} KOPAL 1

20406080100120140160180 ppm

41.67

76.84

77.16

77.48

79.65

111.51

114.55

119.06

120.09

121.73

122.83

126.22

127.70

127.90

129.06

136.61

139.30 Current Data Parameters

NAME KV-V-727EXPNO 2PROCNO 1

F2 - Acquisition ParametersDate_ 20161024Time 13.03INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zgpg30TD 65536SOLVENT CDCl3NS 1024DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 28.5DW 20.800 usecDE 6.00 usecTE 293.1 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1

======== CHANNEL f1 ========NUC1 13CP1 9.15 usecPL1 0.00 dBSFO1 100.6228298 MHz

======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL12 14.90 dBPL13 14.90 dBPL2 -3.00 dBSFO2 400.1316005 MHz


C13CPD CDCl3 {D:\CRR} KOPAL 1

S15

11 10 9 8 7 6 5 4 3 2 1 ppm

3.831

4.867

4.889

4.898

4.921

4.935

4.952

4.967

4.984

5.507

5.524

5.528

5.546

6.736

6.755

6.773

6.831

6.852

6.970

6.988

7.007

7.015

7.023

7.083

7.101

7.121

7.130

7.133

7.151

7.170

7.240

7.260

7.383

7.403

8.017

3.01

2.00

0.97

0.99

1.01

2.89

1.05

1.19

1.07

1.01

0.83

Current Data ParametersNAME KV-V-788-AEXPNO 1PROCNO 1

F2 - Acquisition ParametersDate_ 20170314Time 16.05INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zg30TD 65536

SOLVENT CDCl3NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 144DW 60.800 usecDE 6.00 usecTE 293.1 KD1 1.00000000 secTD0 1


F2 - Processing parametersSI 32768SF 400.1300409 MHzWDW EMSSB 0LB 0.30 Hz

GB 0PC 1.00


20406080100120140160180 ppm

35.62

55.65

76.84

77.16

77.48

78.23

110.91

111.39

114.00

119.21

119.84

120.90

122.09

122.57

126.63

127.30

128.77

129.06

136.51


NAME KV-V-788-AEXPNO 2PROCNO 1






S16

10 9 8 7 6 5 4 3 2 1 ppm

3.763

4.907

4.928

4.939

4.960

5.027

5.046

5.059

5.078

5.147

5.167

5.187

6.783

6.784

6.789

6.804

6.810

6.873

6.929

6.949

7.028

7.034

7.066

7.086

7.104

7.180

7.182

7.200

7.218

7.220

7.228

7.247

7.260

7.267

7.343

7.364

7.464

7.484

8.139

3.00

1.03

1.04

0.99

1.01

1.03

1.02

1.02

0.99

1.34

1.04

0.97

1.01

0.85






200 180 160 140 120 100 80 60 40 20 ppm

41.62

55.33

76.84

77.16

77.48

79.56

111.51

112.61

114.13

114.38

119.01

120.07

120.14

121.72

122.81

126.21

130.06

136.57

140.92


NAME KV-V-825

EXPNO 5

PROCNO 1

F2 - Acquisition Parameters

Date_ 20170319

Time 11.00

INSTRUM spect

PROBHD 5 mm DUL 13C-1

PULPROG zgpg30

TD 65536

SOLVENT CDCl3

NS 512

DS 4

SWH 24038.461 Hz

FIDRES 0.366798 Hz

AQ 1.3631988 sec

RG 50.8

DW 20.800 usec

DE 6.00 usec

TE 290.5 K

D1 2.00000000 sec

d11 0.03000000 sec

DELTA 1.89999998 sec

TD0 1

======== CHANNEL f1 ========

NUC1 13C

P1 9.15 usec

PL1 0.00 dB

SFO1 100.6228298 MHz

======== CHANNEL f2 ========

CPDPRG2 waltz16

NUC2 1H

PCPD2 90.00 usec

PL12 14.90 dB

PL13 14.90 dB

PL2 -3.00 dB

SFO2 400.1316005 MHz

F2 - Processing parameters

SI 32768

SF 100.6127577 MHz

WDW EM

SSB 0

LB 1.00 Hz

GB 0

PC 1.40


S17

2345678910 ppm3.775

4.873

4.894

4.904

4.925

5.026

5.044

5.056

5.075

5.121

5.141

6.838

6.844

6.855

6.860

6.868

7.023

7.029

7.056

7.058

7.076

7.094

7.096

7.178

7.181

7.199

7.216

7.219

7.237

7.242

7.255

7.260

7.351

7.372

7.425

7.445

8.103

3.06

1.00

1.00

1.01

1.88

0.96

1.03

1.07

2.25

0.96

0.97

0.90






200 180 160 140 120 100 80 60 40 20 ppm

40.97

55.37

76.84

77.16

77.48

79.87

111.50

114.39

114.86

119.11

120.04

121.58

122.79

126.21

128.95

131.29

136.62








S18

13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

4.935

4.949

4.960

4.967

4.982

4.992

5.014

5.716

5.736

5.738

5.756

7.059

7.060

7.078

7.097

7.106

7.110

7.117

7.120

7.128

7.140

7.180

7.182

7.192

7.202

7.217

7.220

7.260

7.341

7.343

7.359

7.361

7.363

7.425

7.444

7.620

7.640

8.221

2.12

1.00

3.15

3.05

1.06

1.04

1.04

0.91






20406080100120140160180 ppm

40.72

76.84

77.16

77.48

77.90

111.51

113.44

119.12

120.12

122.07

122.89

124.60

126.31

128.03

129.25

133.59

136.60








S19

9 8 7 6 5 4 3 2 1 ppm

0.000

4.781

4.802

4.813

4.834

4.913

4.932

4.945

4.964

5.042

5.061

5.081

6.912

6.917

7.005

7.024

7.071

7.090

7.105

7.110

7.123

7.142

7.159

7.176

7.196

7.253

7.273

7.289

7.308

7.327

7.347

7.374

7.378

7.382

8.068

0.99

1.00

0.98

0.96

1.00

2.10

1.19

1.04

1.01

1.00

0.98

0.94


F2 - Acquisition ParametersDate_ 20171124Time 16.02INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zg30TD 65536SOLVENT CDCl3NS 16

DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 128DW 60.800 usecDE 6.00 usecTE 294.7 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 11.42 usec

PL1 -3.00 dBSFO1 400.1324710 MHz



406080100120140160180200 ppm

41.23

76.84

77.16

77.48

79.26

111.62

113.71

118.83

120.22

121.70

122.97

123.10

126.00

126.57

130.59

130.91

130.96

136.57


NAME KV-VI-998EXPNO 2PROCNO 1

F2 - Acquisition ParametersDate_ 20171124Time 16.08INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zgpg30TD 65536

SOLVENT CDCl3NS 389DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 57DW 20.800 usecDE 6.00 usecTE 295.5 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 sec

TD0 1


======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usec

PL12 14.90 dBPL13 14.90 dBPL2 -3.00 dBSFO2 400.1316005 MHz



S20

9 8 7 6 5 4 3 2 1 ppm

0.072

4.882

4.904

4.914

4.935

5.031

5.050

5.062

5.081

5.135

5.155

5.175

7.021

7.027

7.068

7.087

7.106

7.196

7.204

7.209

7.213

7.225

7.231

7.260

7.364

7.385

7.387

7.389

7.410

7.437

7.458

8.158

1.06

1.00

0.98

0.93

1.03

3.11

2.09

1.83

0.84






20406080100120140160180 ppm

41.14

76.84

77.16

77.48

79.31

111.61

113.96

118.91

120.23

121.66

123.00

125.99

129.63

129.78

132.19

136.62



F2 - Acquisition ParametersDate_ 20170313Time 13.20INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zgpg30TD 65536SOLVENT CDCl3NS 512DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 32DW 20.800 usecDE 6.00 usecTE 293.2 KD1 2.00000000 secd11 0.03000000 secDELTA 1.89999998 secTD0 1





S21

10 9 8 7 6 5 4 3 2 1 ppm

4.946

4.964

4.978

4.990

4.996

5.012

5.023

5.044

5.732

5.752

5.772

7.066

7.068

7.086

7.106

7.113

7.142

7.146

7.161

7.165

7.171

7.179

7.183

7.186

7.191

7.205

7.210

7.225

7.228

7.234

7.260

7.349

7.370

7.423

7.433

7.453

8.135

1.97

1.00

2.06

4.26

1.01

2.04

0.92

Current Data Parameters

NAME KV-VI-925

EXPNO 1

PROCNO 1


Date_ 20170828

Time 12.44

INSTRUM spect


PULPROG zg30

TD 65536

SOLVENT CDCl3

NS 16

DS 2

SWH 8223.685 Hz

FIDRES 0.125483 Hz

AQ 3.9846387 sec

RG 203

DW 60.800 usec

DE 6.00 usec

TE 294.2 K

D1 1.00000000 sec

TD0 1

======== CHANNEL f1 ========

NUC1 1H

P1 11.42 usec

PL1 -3.00 dB

SFO1 400.1324710 MHz


SI 32768

SF 400.1300050 MHz

WDW EM

SSB 0

LB 0.30 Hz

GB 0

PC 1.00


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

38.08

76.84

77.16

77.48

77.82

111.51

113.37

119.06

120.15

122.08

122.92

126.29

127.41

128.98

129.10

130.27

133.97


NAME KV-VI-925

EXPNO 2

PROCNO 1


Date_ 20170830

Time 12.26

INSTRUM spect


PULPROG zgpg30

TD 65536

SOLVENT CDCl3

NS 512

DS 4

SWH 24038.461 Hz

FIDRES 0.366798 Hz

AQ 1.3631988 sec

RG 57

DW 20.800 usec

DE 6.00 usec

TE 293.2 K

D1 2.00000000 sec

d11 0.03000000 sec


TD0 1

======== CHANNEL f1 ========

NUC1 13C

P1 9.15 usec

PL1 0.00 dB

SFO1 100.6228298 MHz

======== CHANNEL f2 ========

CPDPRG2 waltz16

NUC2 1H

PCPD2 90.00 usec

PL12 14.90 dB

PL13 14.90 dB

PL2 -3.00 dB

SFO2 400.1316005 MHz


SI 32768

SF 100.6127578 MHz

WDW EM

SSB 0

LB 1.00 Hz

GB 0

PC 1.40


S22

1234567891011 ppm

4.904

4.925

4.935

4.956

5.036

5.055

5.068

5.087

5.163

5.183

5.203

7.046

7.048

7.052

7.090

7.092

7.107

7.110

7.127

7.130

7.210

7.212

7.230

7.233

7.247

7.251

7.256

7.260

7.270

7.324

7.329

7.373

7.393

7.431

7.433

7.451

7.453

8.161

1.00

1.00

0.98

0.96

1.00

0.82

3.21

0.96

1.00

1.00

0.78


NAME KV-V-868

EXPNO 5

PROCNO 1


Date_ 20170713

Time 11.32

INSTRUM spect


PULPROG zg30

TD 65536

SOLVENT CDCl3

NS 16

DS 2

SWH 8223.685 Hz

FIDRES 0.125483 Hz

AQ 3.9846387 sec

RG 228

DW 60.800 usec

DE 6.00 usec

TE 294.6 K

D1 1.00000000 sec

TD0 1

======== CHANNEL f1 ========

NUC1 1H

P1 11.42 usec

PL1 -3.00 dB

SFO1 400.1324710 MHz


SI 32768

SF 400.1300012 MHz

WDW EM

SSB 0

LB 0.30 Hz

GB 0

PC 1.00


200 180 160 140 120 100 80 60 40 20 0 ppm

41.29

76.84

77.16

77.48

79.28

111.61

113.82

118.88

120.26

121.68

123.02

126.03

126.12

128.01

128.09

130.32

134.91

136.60


NAME KV-V-868

EXPNO 6

PROCNO 1


Date_ 20170717

Time 13.27

INSTRUM spect


PULPROG zgpg30

TD 65536

SOLVENT CDCl3

NS 1024

DS 4

SWH 24038.461 Hz

FIDRES 0.366798 Hz

AQ 1.3631988 sec

RG 57

DW 20.800 usec

DE 6.00 usec

TE 294.8 K

D1 2.00000000 sec

d11 0.03000000 sec


TD0 1

======== CHANNEL f1 ========

NUC1 13C

P1 9.15 usec

PL1 0.00 dB

SFO1 100.6228298 MHz

======== CHANNEL f2 ========

CPDPRG2 waltz16

NUC2 1H

PCPD2 90.00 usec

PL12 14.90 dB

PL13 14.90 dB

PL2 -3.00 dB

SFO2 400.1316005 MHz


SI 32768

SF 100.6127566 MHz

WDW EM

SSB 0

LB 1.00 Hz

GB 0

PC 1.40


S23

2345678910 ppm

1.181

4.797

4.818

4.828

4.849

4.945

4.964

4.977

4.995

5.064

5.084

5.104

6.927

6.932

6.986

6.988

7.005

7.023

7.025

7.111

7.113

7.131

7.149

7.151

7.172

7.175

7.193

7.202

7.218

7.224

7.273

7.293

7.309

7.329

8.076

1.00

1.00

0.98

1.00

1.03

1.08

4.19

2.05

0.77






30405060708090100110120130140150160170180 ppm

41.09

76.86

77.17

77.49

79.42

111.62

114.07

118.94

120.24

121.66

123.01

126.02

129.26

129.29

133.56

136.63








S24

11 10 9 8 7 6 5 4 3 2 1 ppm

4.880

4.901

4.911

4.932

5.034

5.053

5.066

5.084

5.161

5.181

5.201

6.989

6.994

7.014

7.016

7.027

7.032

7.073

7.075

7.091

7.093

7.111

7.113

7.197

7.200

7.218

7.220

7.235

7.238

7.260

7.286

7.292

7.299

7.304

7.308

7.316

7.321

7.354

7.375

7.402

7.403

7.422

7.423

8.137

1.00

1.00

0.98

2.82

0.99

1.01

2.00

1.03

0.98

0.84

Current Data ParametersNAME KV-VI-992-AEXPNO 3PROCNO 1

F2 - Acquisition ParametersDate_ 20171116Time 17.05INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zg30TD 65536SOLVENT CDCl3NS 16

DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 144DW 60.800 usecDE 6.00 usecTE 295.8 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 11.42 usec

PL1 -3.00 dBSFO1 400.1324710 MHz



406080100120140160180 ppm

40.98

76.83

77.14

77.46

79.65

111.57

114.34

115.83

116.04

118.95

120.15

121.56

122.93

126.05

129.44

129.52

135.04

135.07

136.62

160.96


NAME KV-VI-992-AEXPNO 2PROCNO 1



TD0 1






S25

14 13 12 11 10 9 8 7 6 5 4 3 2 1 ppm

5.002

5.024

5.087

5.104

5.119

5.136

5.282

5.302

5.322

7.075

7.077

7.082

7.083

7.093

7.094

7.097

7.112

7.114

7.204

7.206

7.222

7.225

7.227

7.242

7.245

7.260

7.374

7.377

7.380

7.382

7.393

7.395

7.397

7.400

7.482

7.502

7.522

7.699

7.719

8.107

8.109

8.112

8.114

8.127

8.130

8.133

8.135

8.201

8.206

8.211

8.294

1.02

1.00

0.96

1.97

0.99

1.95

0.99

0.99

0.96

0.93

0.80


F2 - Acquisition ParametersDate_ 20171122Time 17.16INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zg30TD 65536

SOLVENT CDCl3NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 144DW 60.800 usecDE 6.00 usecTE 295.0 KD1 1.00000000 secTD0 1


F2 - Processing parametersSI 32768SF 400.1300051 MHzWDW EMSSB 0LB 0.30 Hz

GB 0PC 1.00


30405060708090100110120130140150160170 ppm

41.21

76.84

77.16

77.48

78.97

111.79

113.11

118.58

120.41

121.72

122.80

122.89

123.20

125.76

130.08

134.23

136.62

141.72


NAME KV-VI-996EXPNO 2PROCNO 1



TD0 1






S26

23456789 ppm

2.322

4.900

4.921

4.931

4.952

5.029

5.048

5.060

5.079

5.143

5.163

5.183

7.003

7.008

7.009

7.069

7.072

7.087

7.089

7.107

7.109

7.125

7.145

7.185

7.187

7.205

7.207

7.220

7.240

7.260

7.337

7.357

7.454

7.474

8.091

3.00

1.01

1.01

1.00

0.97

1.02

2.06

3.09

1.05

1.03

0.90


NAME KV-VI-923

EXPNO 1

PROCNO 1


Date_ 20170828

Time 12.52

INSTRUM spect


PULPROG zg30

TD 65536

SOLVENT CDCl3

NS 16

DS 2

SWH 8223.685 Hz

FIDRES 0.125483 Hz

AQ 3.9846387 sec

RG 144

DW 60.800 usec

DE 6.00 usec

TE 294.0 K

D1 1.00000000 sec

TD0 1

======== CHANNEL f1 ========

NUC1 1H

P1 11.42 usec

PL1 -3.00 dB

SFO1 400.1324710 MHz


SI 32768

SF 400.1300050 MHz

WDW EM

SSB 0

LB 0.30 Hz

GB 0

PC 1.00


200 180 160 140 120 100 80 60 40 20 ppm

21.17

41.31

76.84

77.16

77.48

79.75

111.49

114.69

119.06

120.02

121.66

122.75

126.22

127.73

129.71

136.25

136.59


NAME KV-VI-923

EXPNO 2

PROCNO 1


Date_ 20170830

Time 16.06

INSTRUM spect


PULPROG zgpg30

TD 65536

SOLVENT CDCl3

NS 423

DS 4

SWH 24038.461 Hz

FIDRES 0.366798 Hz

AQ 1.3631988 sec

RG 64

DW 20.800 usec

DE 6.00 usec

TE 293.9 K

D1 2.00000000 sec

d11 0.03000000 sec


TD0 1

======== CHANNEL f1 ========

NUC1 13C

P1 9.15 usec

PL1 0.00 dB

SFO1 100.6228298 MHz

======== CHANNEL f2 ========

CPDPRG2 waltz16

NUC2 1H

PCPD2 90.00 usec

PL12 14.90 dB

PL13 14.90 dB

PL2 -3.00 dB

SFO2 400.1316005 MHz


SI 32768

SF 100.6127593 MHz

WDW EM

SSB 0

LB 1.00 Hz

GB 0

PC 1.40


S27

11 10 9 8 7 6 5 4 3 2 1 ppm

5.098

5.111

5.116

5.131

6.066

6.085

6.105

7.024

7.029

7.047

7.049

7.067

7.085

7.086

7.188

7.190

7.208

7.226

7.228

7.260

7.360

7.383

7.396

7.439

7.459

7.505

7.520

7.522

7.539

7.544

7.549

7.562

7.566

7.569

7.583

7.785

7.797

7.809

7.891

7.895

7.914

8.106

8.274

8.295

2.07

1.00

2.02

1.12

3.19

1.17

2.10

1.02

1.16

0.85

0.96


F2 - Acquisition ParametersDate_ 20170508Time 11.31INSTRUM spectPROBHD 5 mm DUL 13C-1PULPROG zg30TD 65536SOLVENT CDCl3

NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 228DW 60.800 usecDE 6.00 usecTE 291.8 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========

NUC1 1HP1 11.42 usecPL1 -3.00 dBSFO1 400.1324710 MHz



180 160 140 120 100 80 60 40 20 ppm

37.13

76.84

77.16

77.48

78.64

111.56

114.47

118.97

120.14

122.77

122.82

122.87

124.79

125.50

126.08

126.27

127.01

128.49

129.31

131.24

134.30

134.73








S28

234567891011 ppm

5.033

5.054

5.064

5.085

5.123

5.142

5.155

5.173

5.352

5.372

5.391

7.045

7.047

7.065

7.085

7.181

7.199

7.216

7.218

7.260

7.346

7.366

7.422

7.426

7.443

7.447

7.469

7.479

7.489

7.492

7.790

7.798

7.803

7.812

8.120

1.00

0.97

0.99

1.91

1.21

1.04

4.05

3.96

0.93






30405060708090100110120130140150160170 ppm

41.79

76.86

77.17

77.49

79.54

111.54

114.49

119.07

120.15

121.90

122.87

125.94

126.24

126.27

126.49

126.55

127.81

128.03

128.93

132.89

133.57

136.65








S29

9 8 7 6 5 4 3 2 1 ppm

0.070

4.902

4.920

4.933

4.951

5.036

5.056

5.067

5.088

5.238

5.258

5.277

6.163

6.171

6.307

6.312

6.315

6.319

7.120

7.142

7.149

7.156

7.209

7.227

7.246

7.260

7.377

7.387

7.390

7.397

7.554

7.574

8.157

0.97

1.00

0.97

0.89

0.88

2.09

0.99

1.91

0.96

0.83






180 160 140 120 100 80 60 40 20 ppm

35.84

76.84

77.16

77.48

78.00

107.52

110.60

111.66

111.76

118.84

120.21

122.79

122.84

125.82

136.44

142.39








S30

10 9 8 7 6 5 4 3 2 1 0 ppm

0.072

4.968

4.988

4.999

5.020

5.033

5.052

5.064

5.083

5.450

5.470

5.489

6.937

6.946

6.949

6.958

6.990

6.999

7.101

7.119

7.128

7.135

7.195

7.197

7.207

7.210

7.223

7.241

7.243

7.260

7.372

7.393

7.513

7.532

8.161

2.15

1.00

1.00

1.06

2.17

2.09

1.01

1.05

0.83






20406080100120140160180 ppm

37.05

76.84

77.16

77.48

80.13

111.65

114.16

118.94

120.20

122.09

122.89

125.04

125.39

125.83

127.09

136.52








S31

11 10 9 8 7 6 5 4 3 2 1 ppm

3.773

4.911

4.932

4.942

4.963

5.024

5.043

5.055

5.074

5.121

5.141

5.161

6.842

6.848

6.863

6.869

6.999

7.005

7.230

7.231

7.239

7.252

7.260

7.266

7.269

7.275

7.282

7.295

7.305

7.311

7.319

7.325

7.332

7.339

7.353

8.041

3.00

1.12

1.13

1.08

2.16

1.01

1.92

3.85

0.93






405060708090100110120130140150160170 ppm

41.65

55.97

76.84

77.16

77.48

79.61

100.96

112.23

112.86

114.20

122.41

126.69

127.70

127.89

129.05

131.71

139.27








S32

3456789 ppm4.835

4.855

4.866

4.886

4.937

4.957

4.968

4.988

5.047

5.067

5.087

6.995

7.001

7.141

7.163

7.198

7.202

7.215

7.219

7.223

7.232

7.236

7.241

7.253

7.260

7.268

7.276

7.279

7.293

7.297

7.300

7.489

7.493

8.144

1.02

1.00

0.98

0.99

1.03

6.59

1.06

1.00






20406080100120140160180 ppm

41.41

76.84

77.16

77.48

79.52

112.99

113.35

114.12

121.57

122.87

125.77

127.78

127.89

127.97

129.18

135.21








S33

3. HPLC chromatogram of compounds, 3a-3s

S34

HPLC chromatogram of 3a

Data Graph

Minutes

20 21 22 23 24 25 26 27 28 29 30 31 32

Vo

lts

0.0

0.1

0.2

0.3

2

3.7

42

15374338

2

7.4

50

15493525

Detector A (215nm)744-2 racemic1 (70,30,H,IPA,0.9ml,OD-H) 744-2 racemic1 (70,30,H,IPA,0001.9ml,OD-H)

NameRetention TimeArea

Run Report Detector A (215nm)

Pk # Name Retention Time

Area Height Units Area Percent

Integration Codes

1 23.742 15374338 304685 49.81 MM 2 27.450 15493525 265447 50.19 MM

Totals 30867863 570132 100.00

S35

Data Graph

Minutes

22 23 24 25 26 27 28 29 30 31 32

Vo

lts

0.0

0.5

1.0

1.5

2

4.6

50

11890076

2

8.0

92

108322092

Detector A (215nm)764 (70,30,H,IPA,0.9ml,OD-H) 764 (70,30,H,IPA,0001.9ml,OD-H)





Integration Codes

1 24.650 11890076 227370 9.89 MM 2 28.092 108322092 1709995 90.11 MM

Totals 120212168 1937365 100.00

S36

HPLC chromatogram of 3b

Data Graph

Minutes

10 11 12 13 14 15 16 17 18 19 20

Vo

lts

0.00

0.25

0.50

0.75

1.00

1.25

1

3.4

33

37751419

1

6.5

33

37848956

Detector A (215nm)KV-V- 772-2 OME RAC(70,30,H,IPA,0.9ml,OD-H) KV-V- 772-2 OME RAC(70,30,H,IPA,0001.9ml,OD-H)





Integration Codes

1 13.433 37751419 1296054 49.94 MM 2 16.533 37848956 1032740 50.06 MM

Totals 75600375 2328794 100.00

S37

Data Graph

Minutes

10 11 12 13 14 15 16 17 18 19 20

Vo

lts

0.0

0.5

1.0

1.5

1

3.4

08

45463432

1

6.5

08

4664968

Detector A (215nm)KV-V- 788-2 OME(70,30,H,IPA,0.9ml,OD-H) KV-V- 788-2 OME(70,30,H,IPA,0001.9ml,OD-H) -H)


Run Report

Detector A (215nm) Pk # Name Retention

Time Area Height Units Area

Percent Integration Codes

1 13.408 45463432 1575641 90.69 MM 2 16.508 4664968 132522 9.31 MM

Totals 50128400 1708163 100.00

S38

HPLC chromatogram of 3c

Data Graph

Minutes

20 22 24 26 28 30 32 34

Vo

lts

0.00

0.25

0.50

0.75

1.00

1.25

2

3.5

67

72

38

81

44

3

1.7

92

73

87

29

01

Detector A (215nm)KV-V--830- 3-methoxy rac(70,30,H,IPA,1ml,OD-H) KV-V--830- 3-methoxy rac(70,30,H,IPA,1ml,OD-H) 001





Integration Codes

1 23.567 72388144 1302427 49.49 MM 2 31.792 73872901 989913 50.51 MM

Totals 146261045 2292340 100.00

S39

Data Graph

Minutes

20 22 24 26 28 30 32 34

Vo

lts

0.0

0.5

1.0

1.5

2

3.5

58

87

40

08

1

3

1.7

75

10

46

08

52

8

Detector A (215nm)KV-V--825- 3-methoxy (70,30,H,IPA,1ml,OD-H) KV-V--825- 3-methoxy (70,30,H,IPA,1ml,OD-H) ) 001





Integration Codes

1 23.558 8740081 166035 7.71 MM 2 31.775 104608528 1353930 92.29 MM

Totals 113348609 1519965 100.00

S40

HPLC chromatogram of 3d

Data Graph

Minutes

22 23 24 25 26 27 28 29 30 31 32

Vo

lts

0.00

0.05

0.10

0.15

2

5.3

33

10433321

2

8.4

00

10460703

Detector A (215nm)KV-V- 778- 4 OME, RAC (70,30,H,IPA,1ml,OD-H) KV-V- 778- 4 OME, RAC (70,30,H,IPA,1ml,OD-H)001





Integration Codes

1 25.333 10433321 175432 49.93 MM 2 28.400 10460703 155170 50.07 MM

Totals 20894024 330602 100.00

S41

Data Graph

Minutes

22 23 24 25 26 27 28 29 30 31 32

Vo

lts

0.00

0.05

0.10

0.15

2

5.4

50

1958149

2

8.4

08

11091929

Detector A (215nm)KV-V- 790- 4 OME (70,30,H,IPA,1ml,OD-H) KV-V- 790- 4 OME (70,30,H,IPA,1ml,OD-H) 001





Integration Codes

1 25.450 1958149 33525 15.00 MM 2 28.408 11091929 167495 85.00 MM

Totals 13050078 201020 100.00

S42

HPLC chromatogram of 3e

Data Graph

Minutes

16 18 20 22 24 26 28 30

Vo

lts

0.00

0.25

0.50

0.75

1.00

1.25

1

7.4

58

50950424

2

6.1

08

51631347

Detector A (215nm)KV-V- 804- 2-bromo rac (70,30,H,IPA,1ml,OD-H) KV-V- 804- 2-bromo rac (70,30,H,IPA,1ml,OD-H) 001





1 17.458 50950424 1266967 49.67 2 26.108 51631347 849369 50.33

Totals 102581771 2116336 100.00

S44

Data Graph

Minutes

16 18 20 22 24 26 28 30

Vo

lts

0.0

0.5

1.0

1.5

2.0

2.5

1

7.3

58

105737673

2

6.1

92

4886257

Detector A (215nm)KV-V- 801- 2-bromo (70,30,H,IPA,1ml,OD-H) KV-V- 801- 2-bromo (70,30,H,IPA,1ml,OD-H) 001





Integration Codes

1 17.358 105737673 2319452 95.58 MM 2 26.192 4886257 82789 4.42 MM

Totals 110623930 2402241 100.00

S45

HPLC chromatogram of 3e (Gram scale reaction)

Data Graph

Minutes

14 16 18 20 22 24 26 28 30 32

Vo

lts

0.0

0.1

0.2

0.3 1

7.1

33

11654233

2

8.0

75

265851

Detector A (220nm)KV-V1-1000-F1-2-br (70.30,H,IPA, 1ml, OD-H)KV-V1-1000-F1-2-br (70001.30,H,IPA, 1ml, OD-H)





Integration Codes

1 17.133 11654233 304521 97.77 MM 2 28.075 265851 5333 2.23 MM

Totals 11920084 309854 100.00

S46

HPLC chromatogram of 3f

Data Graph

Minutes

22 24 26 28 30 32 34 36 38 40 42

Vo

lts

0.0

0.2

0.4

0.6

2

5.5

50

43048878

3

6.4

17

42904317

Detector A (220nm)KV-V1-3-BROMO RAC (70.30,H,IPA, 1 ml, OD-H)KV-V1-3-BROMO RAC (70001.30,H,IPA, 1 ml, OD-H)





Integration Codes

1 25.550 43048878 715912 50.08 MM 2 36.417 42904317 492289 49.92 MM

Totals 85953195 1208201 100.00

S47

Data Graph

Minutes

22 24 26 28 30 32 34 36 38 40 42

Vo

lts

0.00

0.25

0.50

0.75

1.00

2

5.5

58

7088814

3

6.3

92

99041778

Detector A (220nm)KV-V1-998-3 BROMO RAC (70.30,H,IPA, 1 ml, OD-H)KV-V1-998-3 BROMO RAC (70001.30,H,IPA, 1 ml, OD-H)





Integration Codes

1 25.558 7088814 124734 6.68 MM 2 36.392 99041778 1144285 93.32 MM

Totals 106130592 1269019 100.00

S48

HPLC chromatogram of 3g

Data Graph

Minutes

24 26 28 30 32 34 36 38 40

Vo

lts

0.0

0.2

0.4

0.6

0.8

1.0

2

8.6

00

69

68

51

19

3

5.3

67

69

94

66

27

Detector A (215nm)KV-V--829 (70,30,H,IPA,0.9ml,OD-H) KV-V--829 (70,30,H,IPA,0001.9ml,OD-H)





Integration Codes

1 28.600 69685119 1023855 49.91 MM 2 35.367 69946627 817482 50.09 MM

Totals 139631746 1841337 100.00

S49

Data Graph

Minutes

24 26 28 30 32 34 36 38 40

Vo

lts

0.00

0.25

0.50

0.75

1.00

2

8.0

08

78

24

18

1

3

4.6

08

92

03

34

70

Detector A (215nm)KV-V--821- 4-bromo (70,30,H,IPA,1ml,OD-H) KV-V--821- 4-bromo (70,30,H,IPA,1ml,OD-H) 001





Integration Codes

1 28.008 7824181 127636 7.84 MM 2 34.608 92033470 1094653 92.16 MM

Totals 99857651 1222289 100.00

S50

HPLC chromatogram of 3h

Data Graph

Minutes

16 18 20 22 24 26 28 30

Vo

lts

0.0

0.5

1.0

1.5

2.0 1

7.4

00

108109557

2

7.2

83

113373116

Detector A (220nm)KV-VI-926-2-CHLORO RAC (70,30,H,IPA,1.0 ml,OD-H)KV-VI-926-2-CHLORO RAC (70,30,H,IPA,1001.0 ml,OD-H)





Integration Codes

1 17.400 108109557 2303986 48.81 MM 2 27.283 113373116 1700283 51.19 MM

Totals 221482673 4004269 100.00

S51

Data Graph

Minutes

16 18 20 22 24 26 28 30

Vo

lts

0.0

0.5

1.0

1.5

1

7.4

83

64246146

2

7.6

08

3306390

Detector A (220nm)KV-VI-925-2-CHLORO (70,30,H,IPA,1.0 ml,OD-H)KV-VI-925-2-CHLORO (70,30,H,IPA,1001.0 ml,OD-H)





Integration Codes

1 17.483 64246146 1543635 95.11 MM 2 27.608 3306390 59164 4.89 MM

Totals 67552536 1602799 100.00

S52

HPLC chromatogram of 3i

Data Graph

Minutes

22 24 26 28 30 32 34 36

Vo

lts

0.0

0.2

0.4

0.6

2

4.2

58

25817844

3

1.3

67

25256125

Detector A (220nm)KV-V-865 3-chloro rac1 (70,30,H,IPA,1ml,OD-H)KV-V-865 3-chloro rac1 (70,30,H,IPA,1ml,OD-H)001





Integration Codes

1 24.258 25817844 569362 50.55 MM 2 31.367 25256125 321903 49.45 MM

Totals 51073969 891265 100.00

S53

Data Graph

Minutes

22 24 26 28 30 32 34 36

Vo

lts

0.0

0.2

0.4

0.6 2

4.1

17

5423047

3

2.4

75

52427750

Detector A (220nm)KV-V-868 3-chloro (70,30,H,IPA,1ml,OD-H)KV-V-868 3-chloro (70,30,H,IPA,1ml,OD-H)001





Integration Codes

1 24.117 5423047 93401 9.37 MM 2 32.475 52427750 695635 90.63 MM

Totals 57850797 789036 100.00

S54

HPLC chromatogram of 3j

Data Graph

Minutes

24 25 26 27 28 29 30 31 32 33 34 35 36

Vo

lts

0.00

0.05

0.10

0.15

0.20

0.25

2

6.1

58

7086150

3

1.9

08

6866023

Detector A (215nm)KV-V- 799- 4-chloro rac (70,30,H,IPA,1ml,OD-H) KV-V- 799- 4-chloro rac (70,30,H,IPA,1ml,OD-H) 001





Integration Codes

1 26.158 7086150 121478 50.79 MM 2 31.908 6866023 96960 49.21 MM

Totals 13952173 218438 100.00

S55

Data Graph

Minutes

24 25 26 27 28 29 30 31 32 33 34 35 36

Vo

lts

0.0

0.5

1.0

1.5

2

6.0

42

9752378

3

1.2

58

107667620

Detector A (215nm)KV-V- 798- 4-chloro (70,30,H,IPA,1ml,OD-H) KV-V- 798- 4-chloro (70,30,H,IPA,1ml,OD-H) 001





Integration Codes

1 26.042 9752378 173109 8.31 MM 2 31.258 107667620 1413574 91.69 MM

Totals 117419998 1586683 100.00

S56

HPLC chromatogram of 3k

Data Graph

Minutes

20 22 24 26 28 30 32 34

Vo

lts

0.0

0.5

1.0

1.5

2.0

2

2.9

25

142411922

2

9.3

92

140326599

Detector A (220nm)KV-V1-990 4-F RAC (70.30,H,IPA, 1 ml, OD-H)KV-V1-990 4-F RAC (70001.30,H,IPA, 1 ml, OD-H)





Integration Codes

1 22.925 142411922 2268586 50.37 MM 2 29.392 140326599 1977432 49.63 MM

Totals 282738521 4246018 100.00

S57

Data Graph

Minutes

20 22 24 26 28 30 32 34

Vo

lts

0.0

0.5

1.0

1.5

2

3.1

25

12311510

2

9.3

50

132618809

Detector A (220nm)KV-V1-992 4-F (70.30,H,IPA, 1 ml, OD-H)KV-V1-992 4-F (70001.30,H,IPA, 1 ml, OD-H)





Integration Codes

1 23.125 12311510 247683 8.49 MM 2 29.350 132618809 1801035 91.51 MM

Totals 144930319 2048718 100.00

S58

HPLC chromatogram of 3l

Data Graph

Minutes

48 50 52 54 56 58 60 62 64 66 68 70

Vo

lts

0.0

0.1

0.2

0.3

5

1.9

25

50780931

6

2.6

08

50662404

Detector A (220nm)KV-V1-989-3 NITRO RAC (70.30,H,IPA, 1 ml, OD-H)KV-V1-989-3 NITRO RAC (70001.30,H,IPA, 1 ml, OD-H)





Integration Codes

1 51.925 50780931 272925 50.06 MM 2 62.608 50662404 321747 49.94 MM

Totals 101443335 594672 100.00

S59

Data Graph

Minutes

50 52 54 56 58 60 62 64 66 68 70

Vo

lts

0.0

0.1

0.2

0.3

0.4

5

4.4

67

6029578

6

2.0

00

66528404

Detector A (220nm)KV-V1-996-3 NITRO (70.30,H,IPA, 1 ml, OD-H)KV-V1-996-3 NITRO (70001.30,H,IPA, 1 ml, OD-H)





Integration Codes

1 54.467 6029578 45836 8.31 MM 2 62.000 66528404 409924 91.69 MM

Totals 72557982 455760 100.00

S60

HPLC chromatogram of 3m

Data Graph

Minutes

16 17 18 19 20 21 22 23 24 25

Vo

lts

0.0

0.5

1.0

1.5

2.0

2.5

1

8.4

50

122305181

2

1.4

42

126846417

Detector A (220nm)KV-VI-924-4-METHYL RAC 70,30,H,IPA,1.0 ml,OD-H)KV-VI-924-4-METHYL RAC 70,30,H,IPA,1001.0 ml,OD-H)





Integration Codes

1 18.450 122305181 2498915 49.09 MM 2 21.442 126846417 2334296 50.91 MM

Totals 249151598 4833211 100.00

S61

Data Graph

Minutes

16 17 18 19 20 21 22 23 24 25

Vo

lts

0.0

0.2

0.4

0.6

1

8.7

25

4535525

2

1.7

33

32111946

Detector A (220nm)KV-VI-923-4-METHYL 1 (70,30,H,IPA,1.0 ml,OD-H)KV-VI-923-4-METHYL 1 (70,30,H,IPA,1001.0 ml,OD-H)





Integration Codes

1 18.725 4535525 111354 12.38 MM 2 21.733 32111946 642779 87.62 MM

Totals 36647471 754133 100.00

S62

HPLC chromatogram of 3n

Data Graph

Minutes

20 22 24 26 28 30 32 34 36 38 40

Vo

lts

0.00

0.25

0.50

0.75

1.00

1.25

2

3.0

58

75394238

3

3.8

75

76150824

Detector A (215nm)KV-V- 810- 1 NAPH, RAC (70,30,H,IPA,1ml,OD-H) KV-V- 810- 1 NAPH, RAC (70,30,H,IPA,1ml,OD-H) 001





Integration Codes

1 23.058 75394238 1260431 49.75 MM 2 33.875 76150824 858235 50.25 MM

Totals 151545062 2118666 100.00

S63

Data Graph

Minutes

20 22 24 26 28 30 32 34 36 38 40

Vo

lts

0.0

0.5

1.0

1.5

2

3.2

92

70125984

3

4.3

25

10052546

Detector A (215nm)KV-V- 807- 1 NAPH (70,30,H,IPA,1ml,OD-H) KV-V- 807- 1 NAPH (70,30,H,IPA,1ml,OD-H) 001





Integration Codes

1 23.292 70125984 1429080 87.46 MM 2 34.325 10052546 121711 12.54 MM

Totals 80178530 1550791 100.00

S64

HPLC chromatogram of 3o

Data Graph

Minutes

30 35 40 45 50 55 60 65

Vo

lts

0.0

0.1

0.2

0.3

0.4

3

7.0

58

38629796

5

9.0

25

38674445

Detector A (215nm)KV-V- 791- 2 NAPH ,RAC (70,30,H,IPA,0.9ml,OD-H) KV-V- 791- 2 NAPH ,RAC (70,30,H,IPA,0001.9ml,OD-H)


Run Report




1 37.058 38629796 433422 49.97 MM 2 59.025 38674445 266509 50.03 MM

Totals 77304241 699931 100.00

S65

Data Graph

Minutes

35.0 37.5 40.0 42.5 45.0 47.5 50.0 52.5 55.0 57.5 60.0 62.5 65.0

Vo

lts

0.0

0.1

0.2

0.3

0.4

0.5

3

7.0

42

9062660

5

8.9

33

66503739

Detector A (215nm)KV-V- 795- 2 NAPH (70,30,H,IPA,0.9ml,OD-H) KV-V- 795- 2 NAPH (70,30,H,IPA,0001.9ml,OD-H)


Run Report




1 37.042 9062660 102566 11.99 MM 2 58.933 66503739 458084 88.01 MM

Totals 75566399 560650 100.00

S66

HPLC chromatogram of 3p

Data Graph

Minutes

12 14 16 18 20 22 24

Vo

lts

0.0

0.5

1.0

1.5

1

4.9

25

46758246

2

1.7

67

49011649

Detector A (215nm)KV-V-775 -2 furan rac 2 I(70,30,H,IPA,1ml,OD-H) KV-V-775 -2 furan rac 2 I(70,30,H,IPA,1ml,OD-H) 001





Integration Codes

1 14.925 46758246 1475570 48.82 MM 2 21.767 49011649 1030372 51.18 MM

Totals 95769895 2505942 100.00

S67

Data Graph

Minutes

12 14 16 18 20 22 24

Vo

lts

0.0

0.5

1.0

1.5

2.0

1

4.9

33

66095708

2

1.9

08

14777257

Detector A (215nm)KV-V-855 -furan 2 (70,30,H,IPA,1ml,OD-H) KV-V-855 -furan 2 (70,30,H,IPA,1ml,OD-H) 002


Run Report




1 14.933 66095708 1984981 81.73 MM 2 21.908 14777257 315032 18.27 MM

Totals 80872965 2300013 100.00

S68

HPLC chromatogram of 3q

Data Graph

Minutes

20 21 22 23 24 25 26 27 28 29 30

Vo

lts

-0.75

-0.50

-0.25

0.00

0.25

0.50

2

2.2

50

22471889

2

6.1

08

22296069

Detector A (215nm)KV-V-786 -2 thiophene racI(70,30,H,IPA,1ml,OD-H) KV-V-786 -2 thiophene racI(70,30,H,IPA,1ml,OD-H)001





Integration Codes

1 22.250 22471889 467786 50.20 MM 2 26.108 22296069 392018 49.80 MM

Totals 44767958 859804 100.00

S69

Data Graph

Minutes

20 21 22 23 24 25 26 27 28 29 30

Vo

lts

0.0

0.5

1.0

1.5

2.0

2.5

2

2.0

83

121202197

2

6.1

08

28658130

Detector A (215nm)KV-V-856 -2 thiophene I(70,30,H,IPA,1ml,OD-H) KV-V-856 -2 thiophene I(70,30,H,IPA,1ml,OD-H) 001





Integration Codes

1 22.083 121202197 2285854 80.88 MM 2 26.108 28658130 501563 19.12 MM

Totals 149860327 2787417 100.00

S70

HPLC chromatogram of 3r

Data Graph

Minutes

26 28 30 32 34 36 38 40 42

Vo

lts

-0.2

0.0

0.2

0.4

2

8.6

33

21

59

85

87

3

7.7

67

20

67

76

52

Detector A (215nm)KV-V--836- 5-methoxy indole rac (85,15,H,IPA,1ml,OD-H) KV-V--836- 5-methoxy indole rac (85,15,H,IPA,1ml,OD-H)001





Integration Codes

1 28.633 21598587 369081 51.09 MM 2 37.767 20677652 267605 48.91 MM

Totals 42276239 636686 100.00

S71

Data Graph

Minutes

26 28 30 32 34 36 38 40 42

Vo

lts

0.0

0.2

0.4

0.6

0.8

2

8.2

33

45

46

72

58

3

7.8

17

61

86

06

2

Detector A (215nm)KV-V--833- 5-methoxy indole (85,15,H,IPA,1ml,OD-H) KV-V--833- 5-methoxy indole (85,15,H,IPA,1ml,OD-H) 001





Integration Codes

1 28.233 45467258 727072 88.02 MM 2 37.817 6186062 82632 11.98 MM

Totals 51653320 809704 100.00

S72

HPLC chromatogram of 3s

Data Graph

Minutes

16 18 20 22 24 26 28 30

Vo

lts

0.00

0.25

0.50

0.75

1.00

1.25

1

7.2

75

42430703

2

6.2

33

41688078

Detector A (215nm)KV-V-835 -5- bromo indole rac3 (70,30,H,IPA,0.7ml,OD-H) KV-V-835 -5- bromo indole rac3 (70,30,H,IPA,0001.7ml,OD-H)





Integration Codes

1 17.275 42430703 1164735 50.44 MM 2 26.233 41688078 768726 49.56 MM

Totals 84118781 1933461 100.00

S73

Data Graph

Minutes

16 18 20 22 24 26 28 30

Vo

lts

0.0

0.5

1.0

1.5

2.0

1

7.3

50

71071268

2

5.4

92

8564704

Detector A (215nm)KV-V-857 -5- bromo indole (70,30,H,IPA,0.7ml,OD-H) KV-V-857 -5- bromo indole (70,30,H,IPA,0001.7ml,OD-H)





Integration Codes

1 17.350 71071268 2033264 89.25 MM 2 25.492 8564704 166981 10.75 MM

Totals 79635972 2200245 100.00

S74

Comparison of observed and reported optical rotations for 3a-3s

S.

No

Compound Reported

[α]DT

Observed

[α]DT

Reported Observed

Retention time

tR

ee (%) Retention time

tR

ee (%)

1 3aa

[α]D20

= -23.9 [α]D28

= -15.0 tminor = 19.2 min

tmajor = 23.7 min

1.0 ml/min

96%ee

tminor = 24.6 min

tmajor = 28.0 min,

0.9 ml/min

80%ee

2 3ba

[α]D20

= -47.8 [α]D26

= -28.6 tmajor = 16.1 min

tminor = 18.0 min,

0.8 ml/min

95%ee tmajor = 13.4 min

tminor = 16.5 min,

0.9 ml/min

81%ee

3 3ca

[α]D20

= -16.4 [α]D32

= -10.0 tminor = 49.5 min,

tmajor = 70.6 min,

0.5 ml/min

97%ee tminor = 23.5 min,

tmajor = 31.7 min,

1.0 ml/min

84%ee

4 3da

[α]D20

= -28.2 [α]D26

= -11.2 tminor = 31.0 min

tmajor = 35.7 min,

0.8 ml/min

95%ee tminor = 25.4 min

tmajor = 28.4 min,

1.0 ml/min

70%ee

5 3ea [α]D

28 = -79.9 tmajor = 17.3 min,

tminor = 26.1 min

91%ee

6 3fa [α]D

20 = -16.0 [α]D

30 = -13.1 tminor = 21.4 min

tmajor = 30.3 min,

1.0 ml/min


tmajor = 36.3 min,

1.0 ml/min

83%ee

7 3ga [α]D

20= +1.8 [α]D

25= +0.9 tminor = 23.3 min

tmajor = 30.5 min,

1.0 ml/min


tmajor = 34.6 min,

1.0 ml/min

84%ee

8 3ha

[α]D20

= -50.0 [α]D25

= -58.4 tmajor = 14.3min

tminor = 22.7 min,

1.0 ml/min


tminor = 27.6 min,

1.0 ml/min

90%ee

9 3ib

[α]D20

= -18.1 [α]D31

= -14.2 tminor =21.7 min

tmajor = 19.6 min,

1.0 ml/min

92%ee tminor = 24.1min,

tmajor = 32.4 min,

1.0 ml/min

81%ee

10 3ja

[α]D20

= -7.1 [α]D30

= -5.4 tminor = 22.2 min

tmajor = 28.5 min,

1.0 ml/min


tmajor = 31.2 min

1.0 ml/min

83%ee

11 3ka

[α]D20

= -35.0 [α]D30

= -19.3 tminor = 19.5 min,

tmajor = 25.1 min,


tmajor = 29.7 min,

83%ee

S75

1.0 ml/min 1.0 ml/min

12 3la [α]D

20 = -14.8 [α]D

30 = -8.3 tminor = 36.3 min,

tmajor = 50.1 min


tmajor = 62.0 min,

1.0 ml/min

83%ee

13 3ma [α]D

20 = -13.3 [α]D

26 = -8.0 tminor = 15.6 min,

tmajor = 18.8 min


tmajor = 21.7 min,

1.0 ml/min

85%ee

14 3na [α]D

20 = -25.8 [α]D

25 = -13.7 tmajor = 31.1 min

tminor = 39.7 min,

0.8 ml/min


tminor = 34.3 min,

1.0 ml/min

75%ee

15 3oa [α]D

20 = -3.5 [α]D

30 = -2.1 tminor = 48.8 min

tmajor = 61.3 min,

0.8 ml/min


tmajor = 58.9 min,

0.9 ml/min

76%ee

16 3pa [α]D

20 = +38.2 [α]D

32 = +10.0 tmajor = 18.6 min,

tminor = 26.1 min,

0.8 ml/min

95%ee tmajor = 14.9 min,

tminor = 21.9 min,

1.0 ml/min

63%ee

17 3qa [α]D

30 = -25.3 [α]D

25 = -32.0 tmajor = 27.3 min,

tminor = 31.7 min,

0.8 ml/min


tminor = 26.1 min,

1.0 ml/min

61%ee

18 3ra [α]D

30 = +30.2 [α]D

30 = +15.7 tmajor = 16.6 min

tminor = 19.6 min,

0.8 ml/min


tminor = 37.8 min,

1.0 ml/min

76%ee

19 3sa [α]D

30 = +41.0 [α]D

31 = +18.4 tmajor = 15.7 min,

tminor = 20.4 min,

0.8 ml/min


tminor = 25.4 min,

0.7 ml/min

78%ee

a HPLC (Daicel Chiralcel OD-H, hexane/2-propanol = 70:30, b HPLC (Daicel Chiralpak AD-H, hexane/2-

propanol = 90:10

S76

Optimized coordinates and Energies of CRCB TETHERED BIPYRIDINE-Zn--NITROSTYRENE COMPLEX I are given below (in Hartrees): Sum of electronic and zero-point Energies = -2842.571443

Sum of electronic and thermal Energies = -2842.515336

Sum of electronic and thermal Enthalpies = -2842.514391

Sum of electronic and thermal Free Energies = -2842.671105

C -0.67822200 -3.72332000 -0.57301400

C -2.66316100 -2.49196900 -0.15419200

C -3.44265400 -3.61333000 -0.43264900

C -2.81453800 -4.81068700 -0.80748200

C -1.43380000 -4.86999400 -0.87565900

H -4.52190300 -3.55352900 -0.37591000

H -3.41031800 -5.68670700 -1.04449500

H -0.94354800 -5.78857100 -1.17359400

N -1.31152700 -2.55200800 -0.24321100

C -5.06319200 -0.99897400 -1.51406700

C -3.77837800 -0.34902700 -1.04987700

C -5.62944800 -0.35252000 0.76932300

C -6.08217800 -0.96569700 -0.54489000

C -4.11089700 1.04445900 -0.53562500

C -5.08396800 1.03279800 0.47776000

H -6.41074400 -0.34357500 1.53031100

H -3.00916800 -0.32924000 -1.82665500

C -4.41239700 -1.21265800 1.26781100

H -4.75800600 -2.24698900 1.37777900

C -3.25312600 -1.14568400 0.21843300

H -2.44812400 -0.54643800 0.64665500

C -4.00380100 -0.77813800 2.67615700

O -4.78118900 -0.33749800 3.49729800

O -2.69170500 -0.97330400 2.90133000

C -2.15128900 -0.50799300 4.16461700

H -1.14327300 -0.17264200 3.91290200

H -2.74664200 0.34308700 4.50164000

C -2.15075500 -1.62267700 5.19820400

C -3.48326600 2.23121700 -0.90092400

C -3.85931200 3.42398000 -0.27191700

C -4.84322300 3.41770400 0.71872600

C -5.45520300 2.21920500 1.10440600

H -2.69071900 2.23042200 -1.64371700

H -3.36722600 4.35219000 -0.54523600

H -5.12690600 4.34741800 1.20378400

H -6.20380800 2.20921500 1.89178500

C -7.58496400 -2.04531800 -2.09161300

C -7.34248200 -1.48185700 -0.83244000

C -5.29631200 -1.59291200 -2.75202300

C -6.55841900 -2.13013200 -3.03360600

H -8.56943000 -2.44072500 -2.32512900

H -8.13354900 -1.43977700 -0.08790800

S77

H -4.50484100 -1.63352500 -3.49632200

H -6.74736700 -2.58545300 -4.00165700

H -3.17299600 -1.92847900 5.43687800

H -1.59684000 -2.49421100 4.83603500

H -1.67414200 -1.27345500 6.12032100

C 0.78589500 -3.70370400 -0.59299100

C 2.74294700 -2.36438500 -0.50596900

C 3.54880900 -3.49266300 -0.64281300

C 2.94720400 -4.75588100 -0.74963900

C 1.56775400 -4.86448700 -0.72874500

H 4.62691300 -3.39428500 -0.64768400

H 3.56236700 -5.64537900 -0.84390100

H 1.09858900 -5.83801700 -0.79803900

N 1.39289300 -2.48069400 -0.46678800

C 4.99335600 -1.42751000 1.45560700

C 3.71506900 -0.66707200 1.16214100

C 5.67186500 -0.00472500 -0.40899400

C 6.04984900 -1.07591000 0.59594300

C 4.02690500 0.81738800 1.19483400

C 5.09498300 1.17592000 0.35685300

H 6.49802900 0.28271700 -1.06065500

H 2.89940000 -0.93112600 1.84082600

C 4.50310600 -0.60999800 -1.26608900

H 4.88173600 -1.52017900 -1.74568900

C 3.29335100 -0.96246900 -0.33860900

H 2.48344100 -0.26939700 -0.57181900

C 4.14490500 0.32421400 -2.42221800

O 4.92724000 1.09786000 -2.93362500

O 2.87271300 0.15087400 -2.82384200

C 2.37040600 1.03570500 -3.85840900

H 1.31515900 1.16115000 -3.60894800

H 2.88303600 1.99578300 -3.77016800

C 2.57115500 0.42880000 -5.23775700

C 3.33150400 1.78896300 1.90932000

C 3.73265900 3.12570800 1.80883100

C 4.81625900 3.47896900 1.00230200

C 5.49352600 2.50580200 0.25903800

H 2.47412700 1.51086500 2.51620600

H 3.19541000 3.89267300 2.35854300

H 5.12008800 4.51929100 0.93125700

H 6.31237600 2.78365800 -0.39846100

C 7.46926400 -2.68957100 1.69326400

C 7.28231200 -1.71484300 0.70490800

C 5.18328500 -2.39004100 2.44333100

C 6.43097200 -3.01301500 2.56824900

H 8.43260900 -3.18235200 1.78938800

H 8.09600400 -1.45109300 0.03378900

H 4.36954300 -2.65260300 3.11484100

H 6.58683700 -3.75917600 3.34223000

H 3.63602800 0.32634100 -5.46317600

H 2.09853900 -0.55582500 -5.30627200

S78

H 2.12164000 1.07749000 -5.99705100

Zn 0.02241200 -0.95696500 -0.09250900

O -0.17061600 0.51780800 1.26877800

O 0.19272900 0.87399400 -0.92986000

N -0.01375500 1.43139200 0.27970600

C -0.10583900 2.74592100 0.48805900

H -0.32288600 2.97932100 1.52299900

C 0.05360900 3.70782000 -0.49308600

H 0.31816800 3.36075200 -1.48628200

C -0.08803300 5.12681000 -0.29891300

C 0.18733600 6.00600500 -1.37863300

C -0.49504400 5.72849700 0.92189400

C 0.07598300 7.38470100 -1.24628400

H 0.49908600 5.57980000 -2.32927100

C -0.60110000 7.10821100 1.04847300

H -0.73794500 5.10325300 1.77624000

C -0.31713600 7.95388500 -0.03030200

H 0.29876700 8.02320100 -2.09769500

H -0.91475700 7.53205900 1.99951400

H -0.40460000 9.03118300 0.07417300

the royal society of chemistry · s2 data: s. no. details page no. 1. copies of 1h nmr spectra of...

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