Supporting Information 1

S1

Supplemental material for:

Highly chemoselective synthesis of dimeric 2-oxindoles with a C-3/C-5' via Friedel-Crafts alkylations of 2-oxindoles with 3-hydroxy-2-

oxindoles†

K. Naresh Babu,§ Lakshmana K. Kinthada,§ Santanu Ghosh, and Alakesh Bisai*

Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal - 462 066, MP, India

E-Mail: alakesh@iiserb.ac.in

Spectral Graphics

Spectroscopic analysis of all new compounds S2 - S79

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2015

Supporting Information 2

S2

1H NMR (400 MHz, CDCl3) compound ()-6f

13C NMR (100 MHz, CDCl3) compound ()-6f

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

0102030405060708090100110120130140150160170180190f1 (ppm)

Supporting Information 3

S3

Scanned copy of mass spectrum of ()-6f

Supporting Information 4

S4

1H NMR (400 MHz, CDCl3) compound ()-6g

13C NMR (100 MHz, CDCl3) compound ()-6g

Supporting Information 5

S5

Scanned copy of mass spectrum of ()-6g

Supporting Information 6

S6

1H NMR [400 MHz, DMSO-d6:CDCl3 (1:4)] of compound (4a)

13C NMR (100 MHz, CDCl3) compound ()-4a

0102030405060708090100110120130140150160170180190200f1 (ppm)

28.3

400

35.0

783

43.9

779

76.7

299

77.0

476

77.3

653

110.

0251

122.

3304

123.

1241

123.

9133

127.

9765

128.

5727

132.

0010

133.

8055

141.

5779

168.

1662

179.

5236

Supporting Information 7

S7

Scanned copy of mass spectrum of ()-4a

Supporting Information 8

S8

1H NMR (400 MHz, CDCl3) compound ()-4b

13C NMR (100 MHz, CDCl3) compound (±)-4b

1.06

1.07

3.06

1.04

1.08

1.07

1.00

1.05

1.04

0.80

2.16

2.03

2.30

912.

3227

2.33

962.

3577

2.37

312.

3868

2.48

312.

5003

2.51

772.

5335

2.55

292.

5687

3.17

643.

5011

3.51

503.

5287

3.70

733.

7209

3.73

903.

7559

3.76

933.

8909

3.90

913.

9265

3.94

413.

9618

6.71

916.

7385

6.81

856.

8372

6.85

597.

0626

7.08

187.

1010

7.25

227.

2696

7.64

257.

6531

7.66

167.

7141

7.72

167.

7287

26.2

397

27.9

881

34.9

885

43.4

780

76.7

342

77.0

520

77.3

698

108.

1507

122.

2622

122.

9988

123.

4639

127.

8301

127.

9362

131.

9875

133.

7155

144.

2960

168.

0188

176.

7889

Supporting Information 9

S9

Scanned copy of mass spectrum of ()-4b

Supporting Information 10

S10

1H NMR (400 MHz, CDCl3) compound ()-5b

13C NMR (100 MHz, CDCl3) compound (±)-5b

1.12

1.12

0.77

3.00

1.09

1.11

1.00

1.04

1.04

1.01

2.12

2.10

2.29

252.

3073

2.32

232.

3273

2.34

232.

3570

2.53

372.

5509

2.55

422.

5706

2.58

592.

5893

2.60

643.

1466

3.16

123.

6972

3.71

273.

7172

3.73

293.

7478

3.81

813.

8340

3.83

873.

8543

3.86

973.

8744

6.74

156.

7610

6.87

816.

8968

6.91

547.

1139

7.11

597.

1332

7.13

527.

2638

7.34

507.

3631

7.64

717.

6549

7.66

087.

6684

7.67

817.

7164

7.72

407.

7299

7.73

77

26.2

580

33.0

354

35.5

984

75.0

228

76.7

066

77.0

242

77.3

418

108.

7644

123.

0336

123.

1023

123.

7699

129.

2238

129.

7491

131.

9212

133.

7962

143.

4225

168.

0299

177.

0451

Supporting Information 11

S11

Scanned copy of mass spectrum of ()-5b

Supporting Information 12

S12

1H NMR (400 MHz, CDCl3) compound ()-9a

13C NMR (100 MHz, CDCl3) compound (±)-9a

0.0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

5.97

0.98

1.00

4.00

2.99

3.25

97

6.94

226.

9618

7.14

707.

1492

7.16

587.

1678

7.18

457.

1867

7.28

447.

2927

7.29

477.

2989

7.30

327.

3128

7.31

557.

3212

7.32

707.

3312

7.33

287.

3400

7.34

477.

3536

7.39

107.

3981

7.40

227.

4067

7.40

897.

4119

7.41

547.

4174

7.42

267.

4262

7.42

947.

4455

7.44

87

0102030405060708090100110120130140150160170180190f1 (ppm)

Supporting Information 13

S13

Scanned copy of mass spectrum of ()-9a

Supporting Information 14

S14

1H NMR (400 MHz, CDCl3) compound ()-9b

13C NMR (100 MHz, CDCl3) compound ()-9b

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

3.16

3.00

3.17

2.14

1.09

1.10

3.16

1.13

3.20

183.

2038

3.74

78

6.81

336.

8183

6.83

066.

8356

6.89

826.

9177

7.11

867.

1203

7.13

767.

1387

7.15

617.

1577

7.26

017.

2797

7.29

697.

3043

7.30

937.

3215

7.32

667.

3338

7.36

967.

3725

7.38

907.

3918

7.40

837.

4112

26.3

143

39.7

094

39.8

770

40.0

441

40.2

113

40.3

782

52.8

757

55.2

623

78.1

989

78.4

354

78.6

834

83.4

268

108.

9377

113.

7129

123.

2234

125.

4498

127.

7653

130.

2856

130.

8505

144.

3971

159.

5942

175.

0718

Supporting Information 15

S15

Scanned copy of mass spectrum of ()-9b

Supporting Information 16

S16

1H NMR (400 MHz, CDCl3) compound ()-9d

13C NMR (100 MHz, CDCl3) compound (±)-9d

3.05

3.00

3.02

0.99

1.02

2.07

1.04

1.28

1.04

1.01

1.00

3.22

633.

2791

3.67

65

6.85

946.

9022

6.92

167.

0503

7.05

247.

0700

7.08

757.

0900

7.09

587.

1150

7.13

357.

1643

7.16

607.

1845

7.20

207.

2304

7.24

407.

2505

7.37

277.

3751

7.39

207.

3945

7.41

137.

4138

7.45

887.

4771

7.68

417.

7042

26.2

497

32.8

132

52.6

342

76.7

264

77.0

439

77.3

616

81.3

156

108.

3773

109.

3436

112.

1203

119.

7597

121.

5053

122.

0283

122.

9488

125.

4625

137.

7215

144.

1295

175.

1038

Supporting Information 17

S17

Scanned copy of mass spectrum of ()-9d

Supporting Information 18

S18

1H NMR (400 MHz, CDCl3) compound (±)-11a

13C NMR (100 MHz, CDCl3) compound (±)-11a

3.00

1.12

3.03

2.27

3.00

1.06

1.10

1.04

2.63

40

3.23

63

3.78

83

6.86

246.

8844

7.26

007.

2755

7.28

457.

2924

7.34

797.

4303

8.29

338.

3139

26.4

494

55.3

364

76.7

037

77.0

213

77.3

387

77.5

026

114.

1816

116.

9677

124.

8387

126.

0410

127.

0514

130.

3943

131.

3713

139.

9893

160.

0319

170.

7552

178.

0238

Supporting Information 19

S19

Scanned copy of mass spectrum of ()-11a

Supporting Information 20

S20

1H NMR (400 MHz, CDCl3) compound (±)-11b

13C NMR (100 MHz, CDCl3) compound (±)-11b

3.00

1.12

3.08

3.12

1.00

1.13

1.13

1.02

0.96

0.99

0.95

2.60

85

3.44

00

3.84

103.

8644

6.64

356.

6486

6.66

456.

6696

6.75

706.

7780

7.09

627.

1012

7.26

357.

2798

7.29

757.

3574

7.37

377.

3759

7.41

207.

4153

7.43

277.

4513

7.45

468.

2808

8.30

14

26.4

223

55.9

242

55.9

868

76.7

161

77.0

337

77.3

514

77.5

220

109.

0094

110.

9010

116.

9592

118.

4066

124.

8386

126.

0259

130.

2907

130.

4476

131.

7027

139.

9873

149.

2894

149.

5730

170.

8466

177.

8136

Supporting Information 21

S21

Scanned copy of mass spectrum of ()-11b

Supporting Information 22

S22

1H NMR (400 MHz, 0.5 mL CDCl3, 0.1 mL DMSO-D6) of compound (±)-8a

13C NMR (100 MHz, 0.5 mL CDCl3, 0.1 mL DMSO-D6) of compound (±)-8a

2.00

3.13

3.08

8.19

0.93

1.00

2.58

72

3.04

823.

3854

3.76

49

6.79

696.

9796

7.02

097.

0843

7.17

327.

5750

9.97

7010

.220

0

36.1

819

39.1

787

39.3

860

39.5

958

39.8

040

40.0

132

40.2

209

40.4

261

54.9

932

61.5

697

77.2

441

77.5

663

77.8

881

109.

1173

110.

1403

113.

4818

121.

8987

124.

2931

125.

3427

125.

6101

127.

5319

127.

8157

129.

2410

133.

8114

141.

0605

142.

4630

158.

3456

177.

0392

179.

6109

Supporting Information 23

S23

Scanned copy of mass spectrum of ()-8a

Supporting Information 24

S24

1H NMR (400 MHz, 0.3 mL CDCl3, 0.2 mL DMSO-D6) of compound ()-8b

13C NMR (100 MHz, 0.3 mL CDCl3, 0.2 mL DMSO-D6) of compound ()-8b

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

0102030405060708090100110120130140150160170180190200f1 (ppm)

Supporting Information 25

S25

Scanned copy of mass spectrum of ()-8b

Supporting Information 26

S26

1H NMR (400 MHz, CDCl3) of compound ()-8c

13C NMR (100 MHz, CDCl3) of compound ()-8c

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

1.90

3.00

1.03

1.10

1.02

1.01

1.02

2.14

1.01

3.16

0.89

0.91

3.43

93

3.70

93

6.72

886.

7493

6.77

776.

7830

6.79

816.

8033

6.82

786.

8332

6.84

396.

8635

6.94

016.

9594

7.01

577.

0337

7.05

497.

0808

7.12

547.

1707

7.18

447.

1908

7.20

387.

2106

7.22

377.

2297

7.24

448.

8048

9.10

39

0102030405060708090100110120130140150160170180190f1 (ppm)

36.2

440

55.2

434

62.5

558

76.7

055

77.0

231

77.3

406

109.

4295

110.

3421

112.

3469

114.

7749

120.

7277

122.

9378

124.

9742

125.

5750

126.

2442

128.

1681

128.

4181

129.

5323

133.

4578

135.

5933

140.

0228

141.

6973

143.

1503

159.

6352

177.

5186

179.

8095

Supporting Information 27

S27

Scanned copy of mass spectrum of (±)-8c

Supporting Information 28

S28

1H NMR (400 MHz, 0.5 mL CDCl3, 0.1 mL DMSO-D6) of compound ()-8d

13C NMR (100 MHz, 0.5 mL CDCl3, 0.1 mL DMSO-D6) of compound ()-8d

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

0102030405060708090100110120130140150160170180190f1 (ppm)

Supporting Information 29

S29

Scanned copy of mass spectrum of ()-8d

Supporting Information 30

S30

1H NMR (400 MHz, CDCl3) of compound ()-8e

13C NMR (100 MHz, CDCl3) of compound ()-8e

0102030405060708090100110120130140150160170180190f1 (ppm)

Supporting Information 31

S31

Scanned copy of mass spectrum of ()-8e

Supporting Information 32

S32

1H NMR (400 MHz, 0.2 mL CDCl3, 0.3 mL DMSO-D6) of compound ()-8f

13C NMR (100 MHz, 0.5 mL CDCl3, 0.1 mL DMSO-D6) of compound ()-8f

1.94

6.00

3.09

1.13

6.38

0.96

0.96

2.63

20

3.16

32

3.46

65

6.10

986.

1868

6.53

396.

7395

6.76

136.

8139

6.86

936.

9455

7.24

94

9.59

579.

8628

36.1

961

39.4

459

39.6

554

39.8

645

40.0

731

40.2

877

55.0

516

62.2

840

77.2

416

77.5

640

77.8

856

98.3

414

106.

8409

109.

0942

110.

1562

121.

8896

124.

3800

125.

3070

125.

6871

127.

6681

127.

9698

133.

3090

134.

8627

141.

1278

142.

5888

144.

3488

160.

3220

177.

0113

179.

0267

Supporting Information 33

S33

Scanned copy of mass spectrum of ()-8f

Supporting Information 34

S34

1H NMR (400 MHz, CDCl3) of compound ()-8g

13C NMR (100 MHz, CDCl3) of compound (±)-8g

3.00

2.03

1.09

1.10

2.18

0.98

5.01

2.20

0.76

3.29

883.

4635

6.74

366.

7640

6.92

776.

9472

7.06

137.

0824

7.10

167.

1206

7.13

617.

2334

7.25

817.

2742

7.28

707.

3077

7.32

627.

3448

8.10

79

26.7

141

36.2

052

62.1

583

76.7

101

77.0

275

77.3

450

108.

6659

109.

2504

122.

9462

125.

0440

125.

5497

125.

9712

127.

3556

128.

1468

128.

2860

128.

4193

128.

5302

132.

8808

136.

0534

141.

5905

141.

9794

142.

9859

177.

7127

Supporting Information 35

S35

Scanned copy of mass spectrum of ()-8g

Supporting Information 36

S36

1H NMR (400 MHz, CDCl3) of compound ()-8h

13C NMR (100 MHz, CDCl3) of compound ()8h

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

2.92

1.93

3.01

3.10

1.18

7.10

0.90

3.27

423.

4140

3.73

28

6.74

336.

8119

6.92

197.

0578

7.10

827.

1903

7.29

26

9.45

34

0102030405060708090100110120130140150160170180190200f1 (ppm)

26.7

293

36.4

198

55.2

814

61.5

561

76.9

181

77.2

372

77.5

552

108.

7305

109.

6548

113.

9096

122.

9850

124.

7393

125.

6695

125.

8697

127.

9837

128.

3564

129.

5266

133.

3196

133.

8336

142.

8983

158.

8382

178.

1348

178.

2287

Supporting Information 37

S37

Scanned copy of mass spectrum of ()-8h

Supporting Information 38

S38

1H NMR (400 MHz, CDCl3) of compound ()-8i

13C NMR (125 MHz, CDCl3) of compound ()-8i

6.22

2.06

6.15

1.06

1.12

4.08

2.23

4.14

10.0

2

2.00

2.01

0.00

00

1.36

901.

3865

3.33

523.

3533

3.37

213.

3898

3.73

94

6.73

426.

7401

6.75

416.

7595

6.79

796.

8191

6.94

656.

9655

7.00

487.

0234

7.04

177.

1221

7.13

497.

1506

7.17

277.

1841

7.20

407.

2429

9.42

349.

7903

9.80

03

15.1

284

15.1

942

41.2

449

55.2

747

62.2

248

76.8

092

77.0

632

77.3

176

109.

6680

110.

5960

113.

9449

122.

8515

123.

9912

126.

0260

127.

9900

128.

1439

128.

2602

129.

5099

131.

4912

140.

3064

140.

5722

158.

8781

180.

9280

181.

7846

Supporting Information 39

S39

Scanned copy of mass spectrum of ()-8i

Supporting Information 40

S40

1H NMR (400 MHz, CDCl3) of compound (±)-8j

13C NMR (100 MHz, CDCl3) of compound ()-8j

0102030405060708090100110120130140150160170180190200f1 (ppm)

15.1

250

15.1

823

41.0

998

41.1

147

62.7

106

62.7

619

76.7

056

77.0

232

77.3

408

109.

4023

109.

4314

110.

4034

122.

9150

122.

9379

124.

1751

126.

1971

126.

2320

127.

4400

128.

1307

128.

2624

128.

2810

128.

3702

128.

5923

131.

5805

135.

7932

140.

1245

140.

4371

180.

0829

181.

1899

181.

2025

Supporting Information 41

S41

Scanned copy of mass spectrum of ()-8j

Supporting Information 42

S42

1H NMR (400 MHz, 0.3 mL CDCl3, 0.25 mL DMSO-D6) of compound ()-8k

13C NMR (100 MHz, 0.3 mL CDCl3, 0.25 mL DMSO-D6) of compound (±)-8k

3.05

1.90

0.99

2.14

2.90

1.03

0.78

0.87

1.67

83

3.37

703.

4201

6.75

116.

7670

6.93

156.

9470

6.96

806.

9828

7.05

887.

0743

7.08

647.

1665

7.18

147.

1960

10.2

290

10.3

097

Supporting Information 43

S43

Scanned copy of mass spectrum of (±)-8k

Supporting Information 44

S44

1H NMR (400 MHz, 0.3 mL CDCl3, 0.25 mL DMSO-D6) of compound ()-8l

13C NMR (100 MHz, 0.3 mL CDCl3, 0.25 mL DMSO-D6) of compound (±)-8l

5.65

6.02

2.00

0.94

0.85

12.0

0

1.81

1.79

1.39

291.

4058

1.42

401.

7457

2.59

00

3.31

003.

3268

3.34

523.

3629

6.76

146.

7742

6.78

146.

7939

6.96

176.

9805

6.99

387.

0053

7.01

247.

0241

7.03

117.

0449

7.06

887.

0823

7.10

027.

1319

7.15

127.

1879

7.19

327.

2046

7.22

317.

4744

9.75

949.

9307

0102030405060708090100110120130140150160170180190200f1 (ppm)

Supporting Information 45

S45

Scanned copy of mass spectrum of ()-8l

Supporting Information 46

S46

1H NMR (500 MHz, CDCl3) of compound ()-8m

13C NMR (125 MHz, CDCl3) of compound ()-8m

3.03

3.00

2.00

1.03

1.03

3.90

0.95

0.88

1.78

10

3.26

893.

4818

6.77

476.

7894

6.94

866.

9630

7.14

567.

1598

7.18

467.

1970

7.28

667.

3460

7.35

977.

3720

8.81

74

23.8

206

26.5

546

36.3

030

51.8

583

76.8

095

77.0

637

77.3

182

108.

4709

109.

5954

122.

9618

123.

1741

124.

1170

125.

6794

126.

2865

128.

2413

134.

8606

134.

8956

141.

7628

143.

1676

177.

7669

179.

7117

Supporting Information 47

S47

Scanned copy of mass spectrum of (±)-8m

Supporting Information 48

S48

1H NMR (400 MHz, CDCl3) of compound ()-8n

13C NMR (125 MHz, CDCl3) of compound ()-8n

6.11

6.21

6.09

2.13

2.15

2.36

8.12

2.26

1.96

1.42

761.

4432

1.75

02

3.22

963.

3842

3.40

08

6.73

186.

7500

6.90

966.

9268

7.03

817.

0567

7.09

797.

1125

7.16

017.

1865

7.24

637.

3243

8.60

38

15.2

067

24.1

653

26.5

502

41.1

396

51.8

859

76.7

288

77.0

465

77.3

641

108.

4613

109.

4299

122.

3556

122.

9057

124.

1872

126.

2962

128.

2212

131.

6185

134.

7682

134.

9463

140.

4269

143.

2016

179.

6495

181.

2393

Supporting Information 49

S49

Scanned copy of mass spectrum of ()-8n

Supporting Information 50

S50

1H NMR (400 MHz, CDCl3) of compound (±)-8o

13C NMR (100 MHz, CDCl3) of compound (±)-8o

3.20

3.00

1.91

1.08

0.93

2.02

1.00

1.96

0.90

1.82

43

3.19

94

3.49

42

6.76

806.

7805

7.01

457.

1016

7.12

987.

2020

7.26

56

9.11

54

23.5

262

26.2

301

35.8

143

52.4

007

76.7

490

77.0

668

77.3

847

107.

9820

110.

3567

122.

8740

122.

9586

124.

2528

124.

9512

126.

2602

128.

1666

134.

8399

135.

6190

140.

5168

144.

4790

175.

1961

182.

3836

Supporting Information 51

S51

Scanned copy of mass spectrum of ()-8o

Supporting Information 52

S52

1H NMR (400 MHz, CDCl3) of compound ()-8p

13C NMR (125 MHz, CDCl3) of compound ()-8p

3.00

1.98

0.99

1.09

1.22

9.18

1.11

3.15

77

3.43

52

6.70

116.

7185

6.94

936.

9656

7.04

487.

0604

7.15

897.

1794

7.28

41

9.19

56

26.2

555

35.8

257

62.7

873

76.7

778

77.0

956

77.4

136

107.

8520

110.

6591

122.

8646

124.

6878

124.

8225

126.

1137

127.

4471

128.

1730

128.

3295

128.

3569

128.

6064

133.

6429

135.

9633

140.

3898

141.

7836

144.

5207

175.

2758

180.

4665

Supporting Information 53

S53

Scanned copy of mass spectrum of ()-8p

Supporting Information 54

S54

1H NMR (400 MHz, CDCl3) of compound (±)-8q

13C NMR (100 MHz, CDCl3) of compound ()-8q

1.08

1.05

2.93

2.09

1.07

1.01

1.00

0.98

1.01

1.06

1.99

1.02

2.16

2.15

0.98

2.58

292.

6002

2.61

612.

6349

2.64

912.

7705

2.78

942.

8068

2.82

402.

8430

3.10

713.

3335

3.38

913.

4149

3.47

043.

6304

3.64

463.

6488

3.66

453.

6834

3.69

783.

7205

3.73

903.

7566

3.77

403.

7923

6.65

936.

6811

6.94

806.

9674

7.00

397.

1728

7.26

687.

2981

7.35

157.

3700

7.61

427.

6229

7.62

697.

6340

7.69

857.

7061

7.71

117.

7191

8.83

95

26.1

546

34.3

815

34.9

420

35.7

530

55.0

617

76.7

303

77.0

481

77.3

659

107.

8820

110.

6783

122.

7568

122.

9562

123.

1212

124.

8887

125.

2691

126.

5184

128.

4786

131.

5414

131.

9197

133.

0939

133.

7873

140.

9525

144.

5106

167.

9227

175.

0711

180.

1653

Supporting Information 55

S55

Scanned copy of mass spectrum of ()-8q

Supporting Information 56

S56

1H NMR (400 MHz, CDCl3) of compound (±)-8r

13C NMR (100 MHz, CDCl3) of compound ()-8r

6.00

2.34

3.97

4.17

2.00

3.80

4.15

3.97

8.07

3.66

1.70

641.

9925

2.04

482.

1740

2.21

862.

3526

3.77

233.

9118

6.66

176.

6801

6.71

126.

7300

6.90

866.

9506

6.96

747.

0216

7.05

187.

0738

7.08

717.

1220

7.21

427.

2639

7.29

667.

3808

7.63

507.

6887

7.75

118.

8449

8.93

25

0102030405060708090100110120130140150160170180190200f1 (ppm)

23.7

021

24.0

683

28.6

438

28.8

720

35.0

811

35.1

408

43.9

764

44.0

538

52.3

348

52.3

534

76.7

203

77.0

380

77.3

556

109.

8134

109.

9660

110.

3307

122.

7939

123.

2048

128.

1358

131.

9845

132.

0042

133.

8073

133.

8577

133.

8743

134.

8022

135.

3998

140.

3945

140.

8155

168.

1164

168.

1567

179.

6527

179.

6948

182.

1231

182.

2040

Supporting Information 57

S57

Scanned copy of mass spectrum of ()-8r

Supporting Information 58

S58

1H NMR (400 MHz, CDCl3) of compound ()-8s

13C NMR (125 MHz, CDCl3) of compound ()-8s

6.00

2.13

2.20

6.22

2.13

2.06

2.05

2.19

2.30

6.02

3.90

4.05

4.01

1.91

1.61

071.

6152

2.08

522.

1017

2.11

902.

1355

2.15

782.

1769

2.19

462.

2110

2.22

122.

2381

2.25

652.

2826

2.30

032.

3186

2.33

563.

1450

3.31

493.

3867

3.66

813.

6841

3.70

223.

7182

3.73

533.

8026

3.82

203.

8420

3.85

703.

8768

3.89

606.

5874

6.60

786.

6521

6.67

266.

8180

6.83

776.

9819

7.00

007.

0148

7.02

607.

0477

7.07

067.

1081

7.12

637.

1739

7.18

147.

2089

7.22

707.

2447

7.34

027.

5642

7.68

429.

0390

0102030405060708090100110120130140150160170180190200f1 (ppm)

Supporting Information 59

S59

Scanned copy of mass spectrum of (±)-8s

Supporting Information 60

S60

1H NMR (400 MHz, CDCl3) of compound ()-8t

13C NMR (100 MHz, CDCl3) of compound ()-8t

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.00

1.93

3.12

1.01

2.00

1.01

1.16

6.11

0.82

3.19

293.

4686

3.79

56

6.73

496.

7512

6.84

956.

8673

6.97

546.

9909

7.06

317.

0643

7.07

817.

0793

7.09

317.

1866

7.19

247.

2039

7.20

877.

2123

7.22

077.

2318

7.23

647.

2456

7.24

967.

2876

9.32

07

0102030405060708090100110120130140150160170180190200f1 (ppm)

Supporting Information 61

S61

Scanned copy of mass spectrum of (±)-8t

Supporting Information 62

S62

1H NMR (400 MHz, CDCl3) compound (±)8u

13C NMR (100 MHz, CDCl3) compound (±)-8u

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

4.36

1.98

6.07

3.98

2.21

2.29

2.22

2.30

9.98

4.04

4.42

4.28

2.10

1.87

0.00

002.

2238

2.24

302.

2481

2.26

562.

2832

2.30

103.

4414

3.45

733.

4733

3.76

033.

7907

3.80

613.

8158

3.82

363.

8408

3.85

833.

8763

6.71

946.

7393

6.75

936.

8012

6.80

836.

8234

6.83

056.

9520

6.97

197.

0240

7.04

297.

0574

7.07

627.

0982

7.13

057.

1453

7.15

187.

1671

7.19

507.

2134

7.23

087.

2616

7.60

747.

6171

7.62

047.

6286

7.63

807.

7376

7.74

417.

7509

7.75

757.

7642

8.73

868.

7537

8.95

788.

9869

0102030405060708090100110120130140150160170180190200f1 (ppm)

28.7

888

29.6

971

34.9

694

35.1

010

44.1

368

55.2

460

62.0

802

62.1

560

76.7

500

77.0

678

77.3

855

109.

8070

109.

9237

110.

6059

113.

9503

123.

1561

123.

1794

128.

2214

129.

4559

129.

5517

132.

0119

133.

8206

133.

9412

140.

9380

158.

7658

158.

8205

168.

0765

179.

8608

179.

9217

180.

7269

180.

7630

Supporting Information 63

S63

Scanned copy of mass spectrum of ()-8u

Supporting Information 64

S64

1H NMR (400 MHz, CDCl3) compound (±)-8v

13C NMR (100 MHz, CDCl3) compound (±)-8v

2.01

2.10

2.28

1.14

1.13

1.00

4.01

0.90

0.79

0.00

00

2.93

892.

9722

2.99

043.

0114

3.04

513.

5062

4.98

775.

0128

5.06

555.

1077

5.39

515.

4134

5.43

735.

4553

5.47

905.

4979

6.79

916.

8193

6.87

506.

8956

7.17

127.

2120

7.26

23

8.06

728.

1626

36.1

905

41.5

757

56.8

103

76.6

975

77.0

151

77.3

326

109.

6213

110.

9625

120.

0489

123.

4287

125.

6424

125.

8961

126.

6250

128.

0599

128.

4205

131.

5053

132.

8444

134.

1908

139.

2881

141.

8624

177.

1012

179.

7476

Supporting Information 65

S65

Scanned copy of mass spectrum of ()-8v

Supporting Information 66

S66

1H NMR (400 MHz, CDCl3) of compound ()-8w (Major diastereomer)

13C NMR (100 MHz, CDCl3) of compound ()-8w (Major diastereomer)

25.8

161

26.1

585

32.9

603

48.2

172

54.7

999

76.7

380

77.0

557

77.3

735

107.

5354

107.

9691

109.

4572

109.

5920

119.

3432

121.

6084

121.

8696

124.

2794

124.

3827

137.

8825

143.

7316

144.

3407

174.

1668

176.

6199

Supporting Information 67

S67

Scanned copy of mass spectrum of ()-8w (Major diastereomer)

Supporting Information 68

S68

1H NMR (400 MHz, CDCl3) of compound ()-8x (Minor diastereomer)

13C NMR (100 MHz, CDCl3) of compound ()-8x (Minor diastereomer)

25.7

839

26.5

577

32.8

645

49.8

501

53.5

309

76.7

530

77.0

708

77.3

886

107.

6256

108.

4630

109.

5853

111.

2838

121.

9751

122.

2845

125.

4148

128.

4407

128.

8926

138.

0934

144.

7185

145.

2070

174.

0725

176.

8732

Supporting Information 69

S69

Scanned copy of mass spectrum of ()-8x (Minor diastereomer)

Supporting Information 70

S70

1H NMR (400 MHz, CDCl3) compound ()-2a

13C NMR (100 MHz, CDCl3) compound ()-2a

4.21

4.26

2.30

4.15

2.30

2.19

2.15

6.00

2.18

1.99

2.15

8.17

8.23

1.99

1.94

2.32

892.

3661

2.55

842.

5746

3.35

473.

3671

3.45

753.

5999

3.69

873.

7148

3.73

193.

7468

3.86

413.

8778

3.89

45

6.63

956.

6598

6.67

506.

6957

6.91

636.

9306

7.06

797.

0860

7.10

447.

1392

7.15

527.

2461

7.25

317.

2728

7.32

107.

5557

7.65

319.

0879

9.11

909.

2904

0102030405060708090100110120130140150160170180190200f1 (ppm)

28.4

796

28.5

930

34.3

271

34.3

771

34.9

728

35.0

509

35.0

984

35.3

386

44.1

064

44.1

924

55.1

268

55.1

900

76.7

666

77.0

847

77.4

026

109.

9324

110.

1112

110.

8150

122.

6545

123.

0150

123.

1163

123.

1341

131.

8792

131.

9100

131.

9203

131.

9476

133.

7961

141.

0621

141.

0861

141.

1592

167.

9147

168.

0590

179.

7813

179.

8411

180.

3783

180.

4440

Supporting Information 71

S71

Scanned copy of mass spectrum of ()-2a

Supporting Information 72

S72

1H NMR (400 MHz, CDCl3) of compound ()-2b

13C NMR (100 MHz, CDCl3) of compound ()-2b

4.15

4.41

6.00

6.11

2.22

4.38

4.37

3.91

2.21

4.22

4.36

16.1

4

2.24

602.

2663

2.28

082.

2958

2.31

352.

3337

2.35

012.

3651

2.37

992.

4029

2.41

882.

4379

2.45

352.

4740

2.48

892.

5046

2.53

753.

0754

3.16

563.

3447

3.37

453.

4898

3.51

983.

6104

3.64

613.

6921

3.72

263.

7531

3.85

003.

8849

6.53

156.

5523

6.56

446.

5849

6.61

656.

6372

6.78

256.

8020

6.86

346.

8698

7.24

50

7.61

077.

6250

7.63

227.

6385

7.65

327.

6595

7.66

667.

6730

7.67

977.

6888

7.70

197.

7096

7.73

37

0102030405060708090100110120130140150160170180190200f1 (ppm)

26.2

196

26.2

425

26.5

521

26.5

590

28.1

960

28.2

254

34.5

302

34.5

477

34.9

581

34.9

982

35.0

220

35.2

718

43.5

510

43.6

065

54.5

682

54.6

291

76.8

136

77.0

679

77.3

221

107.

7010

108.

1187

108.

8152

122.

0363

122.

4336

122.

5192

122.

6114

122.

8684

122.

8775

123.

0888

124.

6864

124.

8144

126.

3368

126.

8467

128.

0686

128.

2599

128.

2822

128.

5567

131.

9185

131.

9370

131.

9480

132.

0062

133.

5922

133.

6800

133.

6944

133.

7489

133.

8168

143.

5867

143.

6891

143.

7327

167.

7813

167.

9199

167.

9275

176.

8222

176.

8801

Supporting Information 73

S73

Scanned copy of mass spectrum of ()-2b

Supporting Information 74

S74

HPLC data HPLC data of (17) (Racemic)

Supporting Information 75

S75

HPLC data of ()-17:

Supporting Information 76

S76

HPLC data of (9d) (Racemic):

Supporting Information 77

S77

HPLC data of ()-9d:

Supporting Information 78

S78

HPLC data of (8w) (Racemic):

Supporting Information 79

S79

HPLC data of (8w) synthesized from enantioenriched starting material ()-9d (ee = 91%):