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1 Supporting Information Synthesis of C2-tetrasubstituted indolin-3-ones via Cu-catalyzed oxidative dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh, a§ SatheeshvarmaVanaparthi, a§ SachinChoudhary, a RanganKrishnan, b and Indresh Kumar* a a Department of Chemistry, Birla Institute of Technology & Science, Pilani 333 031, India b Department of Chemistry, BITS Pilani, Hyderabad Campus, Secunderabad, India § authors have contributed equally Corresponding Email: [email protected], [email protected] Table of Contents 1 H, 13 C-NMRand HRMS data for the newly synthesized compounds…………….……...…......S2 Single Crystal X-ray and data for 2g…………………………………………………………...S40 Electronic Supplementary Material (ESI) for RSC Advances. This journal is © The Royal Society of Chemistry 2019

Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

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Page 1: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

1

Supporting Information

Synthesis of C2-tetrasubstituted indolin-3-ones via Cu-catalyzed oxidative

dimerization of 2-aryl indoles and cross-addition of indoles

AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band Indresh

Kumar*a

aDepartment of Chemistry, Birla Institute of Technology & Science, Pilani 333 031, India

bDepartment of Chemistry, BITS Pilani, Hyderabad Campus, Secunderabad, India

§authors have contributed equally

Corresponding Email: [email protected], [email protected]

Table of Contents

1H,13C-NMRand HRMS data for the newly synthesized compounds…………….……...…......S2

Single Crystal X-ray and data for 2g…………………………………………………………...S40

Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2019

Page 2: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

2

Figure S1: HRMS confirmation of in situ generated 2-phenyl indole-3-one

N

O

Calcd m/z = 208.0762Found m/z = 208.0757

Page 3: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

Oct02-2017.3.fidINDO1

1.01

1.03

1.02

1.05

1.04

8.21

1.46

1.04

1.02

1.07

2.02

0.97

6.70

6.72

6.78

6.80

6.81

6.91

6.91

6.92

6.93

6.93

6.94

6.95

6.99

7.01

7.13

7.14

7.15

7.16

7.17

7.18

7.19

7.23

7.24

7.24

7.25

7.27

7.27

7.31

7.33

7.39

7.41

7.42

7.44

7.44

7.44

7.46

7.46

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Oct02-2017.4.fidINDO1

72.0

9

110.

7211

2.08

112.

2711

9.19

120.

0012

0.44

121.

5812

2.36

125.

4012

7.25

127.

3912

7.55

127.

6912

8.26

129.

7413

3.26

135.

5513

7.09

137.

1414

0.38

159.

44

200.

34

NH

O

NH2a

NH

O

NH2a

Page 4: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

4

NH

O

NH2a

Page 5: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

Jun28-2017.2.fidIND-03

0.98

7.62

2.07

1.10

2.14

3.09

0.98

5.20

6.78

6.78

6.80

6.81

6.82

6.83

6.84

6.84

6.86

6.86

6.87

6.88

6.88

6.90

6.90

6.91

6.92

6.92

6.94

6.94

7.03

7.05

7.06

7.07

7.14

7.15

7.16

7.16

7.17

7.18

7.18

7.31

7.33

7.34

7.36

7.36

8.16

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Oct02-2017.8.fidINDO3

71.3

9

110.

8811

2.49

112.

6511

4.52

114.

7311

4.95

115.

1611

9.63

120.

2112

0.46

121.

0712

2.61

125.

4112

7.13

128.

9012

8.98

131.

5713

1.66

135.

4813

5.85

135.

8713

6.01

137.

4515

9.26

161.

2016

1.40

163.

6516

3.87

200.

19

NH

O

NH

2bF

F

NH

O

NH

2bF

F

Page 6: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

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NH

O

NH

2bF

F

Page 7: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

7

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

Nov18-2017.1.fidInd09

0.87

2.05

1.97

5.38

2.08

1.15

1.32

1.03

2.19

1.01

5.21

6.86

6.87

6.88

6.89

6.90

6.94

6.95

7.02

7.03

7.05

7.07

7.10

7.10

7.10

7.12

7.12

7.12

7.15

7.16

7.17

7.19

7.19

7.20

7.21

7.21

7.21

7.32

7.34

7.36

7.37

7.37

7.38

7.39

7.39

7.45

7.46

7.50

7.51

7.52

7.53

7.54

7.54

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Nov18-2017.2.fidInd09

71.3

7

111.

0211

2.37

112.

6812

0.08

120.

4212

0.43

120.

9612

2.88

125.

4812

5.80

126.

9812

7.14

127.

7412

7.80

128.

4412

8.89

129.

4612

9.96

133.

6413

4.07

134.

5013

5.57

135.

9313

7.73

141.

9315

9.33

199.

90

NH

O

NH2c

Cl

Cl

NH

O

NH2c

Cl

Cl

Page 8: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

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NH

O

NH2c

Cl

Cl

Page 9: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

9

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

Nov22-2017/1Ind06

1.00

1.87

2.00

1.91

1.86

2.92

2.13

1.94

1.23

1.00

5.20

6.85

6.86

6.87

6.87

6.89

6.91

6.93

6.95

6.97

6.99

7.03

7.05

7.12

7.14

7.17

7.19

7.20

7.22

7.35

7.37

7.39

7.41

7.46

7.49

7.52

7.53

7.54

7.54

8.14

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

Nov22-2017/3Ind06

71.4

0

110.

9211

2.52

119.

7812

0.35

120.

4912

1.07

122.

7812

5.46

127.

1112

7.84

128.

3912

8.65

131.

0613

1.22

132.

0213

3.68

134.

5913

5.55

135.

8113

7.54

138.

6815

9.25

199.

76

NH

O

NH

2dCl

Cl

NH

O

NH

2dCl

Cl

Page 10: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

10

NH

O

NH

2dCl

Cl

Page 11: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

11

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

Oct02-2017.5.fidINDO2

1.00

2.10

2.01

2.22

1.10

2.07

1.40

2.26

1.07

1.06

1.10

1.00

1.01

5.25

6.90

6.91

6.92

6.93

6.96

6.97

7.00

7.02

7.04

7.06

7.10

7.12

7.17

7.19

7.20

7.21

7.26

7.27

7.27

7.33

7.35

7.35

7.36

7.38

7.43

7.45

7.47

7.49

7.53

7.53

7.55

7.56

7.57

7.70

7.71

7.71

8.27

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Oct02-2017.6.fidINDO2

71.3

1

111.

0411

2.35

112.

7112

0.13

120.

3812

0.43

120.

9312

1.82

122.

3412

2.87

125.

5012

6.29

126.

9312

8.18

129.

0912

9.73

129.

9813

0.72

131.

3113

2.79

134.

7513

5.57

135.

9213

7.76

142.

1115

9.34

199.

95

NH

O

NH2e

Br

Br

NH

O

NH2e

Br

Br

Page 12: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

12

NH

O

NH2e

Br

Br

Page 13: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

13

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

Dec23-2017/1IND-15

0.98

0.98

0.99

2.03

6.86

1.25

1.98

2.12

0.98

5.13

6.57

6.59

7.04

7.04

7.12

7.13

7.15

7.18

7.20

7.21

7.22

7.23

7.23

7.23

7.24

7.25

7.29

7.29

7.30

7.31

7.33

7.33

7.33

7.41

7.42

7.43

7.43

7.48

7.50

7.51

8.15

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Dec23-2017/2IND-15

72.5

5

111.

2311

1.45

112.

1711

3.34

113.

7312

1.74

124.

0712

5.43

127.

0612

7.73

127.

9012

8.10

128.

5912

8.77

128.

9412

9.65

132.

6513

4.10

138.

1513

9.51

139.

7215

7.52

198.

61

NH

O

NH

Br

Br

2f

NH

O

NH

Br

Br

2f

Page 14: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

14

NH

O

NH

Br

Br

2f

Page 15: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

15

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

Nov15-2017.1.fidINDO8

3.20

3.11

1.00

0.97

1.04

8.05

1.06

1.02

2.95

1.02

0.96

2.27

2.33

5.17

6.67

6.69

6.76

6.78

6.80

6.91

6.92

6.95

6.99

7.01

7.02

7.04

7.11

7.13

7.15

7.27

7.29

7.35

7.37

7.39

7.41

7.41

7.43

7.45

7.45

8.10

6.66.76.86.97.07.17.27.37.47.5f1 (ppm)

0.97

1.04

8.05

1.06

1.02

2.95

1.02

6.67

6.69

6.76

6.78

6.80

6.91

6.92

6.95

6.99

7.01

7.02

7.04

7.11

7.13

7.15

7.27

7.29

7.35

7.37

7.39

7.41

7.41

7.43

7.45

7.45

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Nov15-2017.2.fidINDO8

21.0

221

.23

71.9

3

110.

6211

1.82

112.

1111

8.88

119.

7712

0.39

121.

6112

2.10

125.

3312

7.10

127.

4812

8.32

128.

9312

9.52

130.

3113

5.45

136.

9313

7.00

137.

1313

7.46

137.

9915

9.14

200.

49

NH

O

NH

H3C

CH3

2g

NH

O

NH

H3C

CH3

2g

Page 16: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

16

NH

O

NH

H3C

CH3

2g

Page 17: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

17

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

Nov24-2017/2IND-10

2.99

3.02

0.99

0.97

2.00

2.95

1.08

6.39

1.16

2.10

0.99

3.56

3.67

5.20

6.64

6.64

6.64

6.69

6.70

6.71

6.71

6.74

6.78

6.79

6.80

6.81

6.82

6.83

6.92

6.94

6.95

7.05

7.07

7.08

7.09

7.10

7.11

7.13

7.15

7.17

7.31

7.33

7.42

7.42

7.44

7.45

7.47

7.47

8.101

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

Nov25-2017/1ind-10

54.9

455

.17

71.9

8

110.

6711

1.70

112.

2111

2.88

113.

1911

4.71

114.

7711

9.21

119.

7412

0.05

120.

4212

1.50

121.

7512

2.38

125.

3812

7.35

128.

8312

9.19

134.

5713

5.41

136.

9913

7.12

141.

9015

8.68

159.

2115

9.38

200.

10

NH

O

NH

OCH3

H3CO

2h

NH

O

NH

OCH3

H3CO

2h

Page 18: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

18

NH

O

NH

OCH3

H3CO

2h

Page 19: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

19

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

Jan15-2018/1IND17

3.03

3.07

1.02

2.10

3.07

1.17

1.17

1.14

2.06

1.10

1.07

4.22

1.00

3.73

3.77

5.18

6.64

6.66

6.71

6.71

6.72

6.73

6.73

6.74

6.76

6.78

6.80

6.90

6.90

6.92

6.92

6.94

6.94

6.97

6.99

7.01

7.03

7.11

7.11

7.13

7.13

7.13

7.15

7.15

7.29

7.31

7.38

7.39

7.41

7.43

7.43

7.44

7.45

7.45

8.07

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Jan15-2018/2IND17

55.2

455

.31

71.6

5

110.

6311

2.19

112.

2411

3.13

113.

6711

9.03

119.

8912

0.53

121.

5012

2.15

125.

4212

5.50

127.

5112

8.44

130.

9713

2.47

135.

4313

6.84

137.

03

159.

0815

9.17

159.

50

200.

67

NH

O

NH

2iH3CO

OCH3

NH

O

NH

2iH3CO

OCH3

Page 20: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

20

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

Dec16-2017/2IND13

3.09

3.17

2.96

3.23

1.12

1.91

1.98

1.00

1.00

2.05

1.98

1.99

1.11

2.16

2.16

2.21

2.30

2.31

4.94

6.65

6.68

6.93

6.95

7.11

7.16

7.24

7.25

7.28

7.35

7.37

7.85

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Dec27-2017/2IND 13

19.2

520

.35

21.3

1

71.7

5

111.

1711

2.12

113.

4011

8.86

121.

0012

1.56

122.

4412

5.02

125.

4912

6.31

128.

9312

9.01

130.

6013

1.11

131.

3213

1.99

132.

0313

4.57

134.

9113

9.78

148.

21

158.

56

199.

34

NH

O

NH

H3C

H3CCH3

CH3

Br

Br 2j

NH

O

NH

H3C

H3CCH3

CH3

Br

Br 2j

Page 21: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

21

NH

O

NH

H3C

H3CCH3

CH3

Br

Br 2j

Page 22: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

Jul17-2019/1MEINDOLE

2.92

2.77

0.98

2.08

1.03

0.99

1.04

1.06

1.05

1.05

1.00

1.95

2.45

5.05

6.89

6.89

6.91

6.91

6.91

6.92

6.93

6.96

6.96

6.98

6.98

6.98

7.00

7.00

7.07

7.08

7.09

7.09

7.10

7.11

7.11

7.25

7.25

7.25

7.27

7.27

7.27

7.41

7.41

7.43

7.43

7.52

7.52

7.53

7.54

7.54

7.55

7.56

7.72

7.72

7.74

7.74

7.90

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Jul19-2019/2INDME

14.5

9

25.0

9

67.1

4

109.

5111

0.43

111.

4911

2.45

119.

0811

9.50

119.

7612

1.27

125.

3212

7.45

132.

5913

4.90

137.

47

159.

55

204.

31

NH

OCH3

NH2k H3C

NH

OCH3

NH2k H3C

Page 23: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

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NH

OCH3

NH2k H3C

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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

Dec12-2017/2INDOLE 4F

0.92

5.10

3.21

1.08

2.96

1.00

0.95

5.36

6.91

6.93

6.94

6.95

6.96

6.98

7.00

7.02

7.03

7.05

7.05

7.15

7.17

7.18

7.19

7.20

7.20

7.22

7.23

7.24

7.40

7.42

7.51

7.52

7.54

7.54

7.56

7.56

7.58

7.71

7.73

8.20

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Dec12-2017/4INDOLE 4F

70.7

4

111.

7111

3.09

115.

1411

5.35

115.

5311

9.58

119.

9212

0.20

122.

7112

3.60

125.

4612

5.66

128.

5612

8.65

135.

3113

6.96

137.

65

160.

51

200.

35

NH

O

NH

F

4ab

NH

O

NH

F

4ab

Page 25: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

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NH

O

NH

F

4ab

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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

Dec16-2017/1INDOLE4CL

0.98

2.02

1.04

2.01

1.06

2.33

1.00

2.99

1.00

0.97

5.35

6.89

6.91

6.93

6.98

6.98

7.00

7.02

7.02

7.12

7.12

7.13

7.13

7.17

7.17

7.19

7.21

7.21

7.24

7.25

7.26

7.26

7.36

7.38

7.49

7.51

7.53

7.53

7.68

7.70

8.26

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Dec16-2017/3INDOLE4CL

70.7

8

111.

7411

3.11

115.

1511

9.45

119.

4611

9.95

120.

1712

2.68

123.

6512

5.34

125.

6012

8.29

128.

5213

3.66

136.

9013

7.70

138.

13

160.

54

200.

16

NH

O

NH

Cl

4ad

NH

O

NH

Cl

4ad

Page 27: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

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NH

O

NH

Cl

4ad

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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

Oct16-2017/1INDOLE3 Br

0.99

2.06

1.06

4.01

2.08

1.00

1.01

1.00

0.94

0.96

5.38

6.92

6.92

6.94

6.94

6.95

6.96

6.97

7.01

7.01

7.03

7.03

7.03

7.05

7.05

7.15

7.16

7.17

7.19

7.21

7.21

7.23

7.23

7.39

7.41

7.41

7.41

7.42

7.43

7.43

7.43

7.44

7.49

7.49

7.49

7.51

7.51

7.51

7.52

7.52

7.54

7.54

7.54

7.56

7.56

7.71

7.73

7.81

7.81

7.82

8.30

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Oct16-2017/2INDOLE3 Br

70.7

6

111.

8011

3.25

115.

0811

9.41

119.

4812

0.07

120.

2612

2.59

122.

7412

3.79

125.

3512

5.66

126.

0612

9.45

130.

0513

0.87

136.

9513

7.80

142.

01

160.

56

199.

92

NH

O

NH4ae

Br

NH

O

NH4ae

Br

Page 29: Supporting Information dimerization of 2-aryl indoles and ... · dimerization of 2-aryl indoles and cross-addition of indoles AnoopSingh,a§SatheeshvarmaVanaparthi,a§SachinChoudhary,aRanganKrishnan,band

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NH

O

NH4ae

Br

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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

Dec07-2017/1INDOLE4CH3

3.05

0.94

2.15

1.09

3.11

2.21

1.13

2.07

1.08

1.02

0.98

2.31

5.39

6.86

6.86

6.88

6.89

6.91

6.96

6.96

6.98

7.00

7.00

7.09

7.10

7.11

7.11

7.14

7.14

7.16

7.16

7.17

7.18

7.18

7.19

7.33

7.35

7.42

7.44

7.47

7.47

7.49

7.49

7.49

7.51

7.51

7.68

7.69

8.29

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Dec08-2017/1INDOLE4CH3

31.6

3

71.2

4

111.

7011

2.87

115.

5011

9.54

119.

5911

9.82

119.

9712

2.45

123.

8312

5.62

125.

6812

6.72

129.

2213

6.52

136.

9813

7.46

137.

54

160.

58

200.

96

CH3

NH

O

NH4ag

CH3

NH

O

NH4ag

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CH3

NH

O

NH4ag

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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

Oct14-2017/1INDOLE2OH

1.29

0.96

6.47

1.11

1.18

2.43

1.06

1.02

1.01

0.98

2.08

5.42

6.90

6.91

6.93

6.94

6.95

6.96

6.96

6.98

6.98

6.99

7.01

7.08

7.10

7.12

7.13

7.14

7.16

7.16

7.24

7.25

7.26

7.26

7.27

7.29

7.56

7.56

7.58

7.58

7.59

7.60

7.60

7.70

7.70

7.72

7.72

7.75

7.77

8.39.

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Oct14-2017/2INDOLE2OH

71.6

2

111.

8711

3.44

113.

7811

8.81

119.

0812

0.15

120.

2512

0.70

122.

5812

4.06

124.

5712

4.96

125.

6912

8.18

129.

9613

6.89

138.

71

156.

08

160.

12

171.

36

204.

04

NH

O

NH

HO

4ak

NH

O

NH

HO

4ak

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NH

O

NH

HO

4ak

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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

Dec01-2017/1INDOLE8

3.00

0.92

0.99

1.01

0.99

0.96

1.00

4.53

1.04

2.00

1.02

0.99

3.63

5.39

6.57

6.58

6.83

6.84

6.86

6.86

6.90

6.92

6.94

6.95

6.97

7.11

7.12

7.26

7.28

7.29

7.30

7.31

7.32

7.34

7.51

7.52

7.53

7.55

7.55

7.61

7.61

7.63

7.63

7.71

7.73

8.14

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Dec01-2017/4INDOLE8

55.5

9

71.2

7

101.

8611

2.27

112.

3111

2.88

115.

4711

9.64

119.

7712

4.46

125.

5112

6.04

126.

8412

7.72

128.

4013

1.99

137.

5213

9.35

154.

02

160.

54

200.

71

NH

O

NH4ba

OCH3

NH

O

NH4ba

OCH3

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NH

O

NH4ba

OCH3

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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)

Dec01-2017/2INDOLE9

2.94

1.04

1.02

1.04

4.04

1.03

1.41

3.10

1.01

1.00

3.65

5.37

6.55

6.55

6.84

6.85

6.86

6.87

6.91

6.93

6.95

6.97

6.98

7.00

7.03

7.09

7.09

7.26

7.28

7.52

7.52

7.54

7.55

7.57

7.58

7.59

7.60

7.71

7.73

8.19

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Dec01-2017/3INDOLE9 55

.66

70.7

9

101.

77

112.

3711

2.43

113.

1011

5.12

115.

2811

5.33

119.

7011

9.93

124.

4112

5.58

125.

9112

8.65

128.

7313

2.05

135.

1613

7.70

154.

13

160.

5916

1.30

163.

74

200.

64

NH

O

NH4bb

OCH3

F

NH

O

NH4bb

OCH3

F

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NH

O

NH4bb

OCH3

F

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0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

Dec21-2017/1INDOLEDM

3.00

3.03

0.99

0.96

1.94

1.04

1.00

0.95

2.18

1.12

0.91

1.12

1.00

1.00

3.62

3.74

5.32

6.58

6.59

6.80

6.81

6.82

6.82

6.83

6.84

6.87

6.89

6.91

6.92

6.94

7.11

7.11

7.17

7.18

7.18

7.19

7.19

7.21

7.23

7.24

7.25

7.27

7.48

7.48

7.50

7.50

7.52

7.52

7.68

7.70

8.01

0102030405060708090100110120130140150160170180190200210f1 (ppm)

Dec23-2017/3INDOLEEDM

55.2

455

.65

71.1

4

101.

91

112.

2211

2.32

112.

8411

2.88

112.

9311

5.51

119.

3411

9.66

119.

8212

4.46

125.

5312

6.07

129.

3713

1.97

137.

4914

1.02

154.

0915

9.63

160.

48

200.

41

NH

O

NH4bh

OCH3

H3CO

NH

O

NH4bh

OCH3

H3CO

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NH

O

NH4bh

OCH3

H3CO

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Crystal structure data for (2g):

Crystal structure of 2-(p-tolyl)-2-(2-(p-tolyl)-1H-indol-3-yl)indolin-3-one(2g):

(CCDC No.1832862)

Single crystals of2-(p-tolyl)-2-(2-(p-tolyl)-1H-indol-3-yl)indolin-3-

oneC61H49Cl3N4O2was selected on aXtaLAB Pro: Kappa dual

offset/far diffractometer. The crystal was kept at 93(2) K during data

collection. Using Olex2,[1] the structure was solved with the ShelXT[2]

structure solution program using Intrinsic Phasing and refined with theShelXL[3] refinement

package using Least Squares minimization.

Crystal Data for C61H49Cl3N4O2 (M =976.39 g/mol): triclinic, space group P-1 (no. 2), a =

13.13930(10) Å, b = 14.65600(10) Å, c = 15.47680(10) Å, α = 110.2300(10)°, β = 91.2620(10)°,

γ = 108.1490(10)°, V = 2629.10(4) Å3, Z = 2, T = 93(2) K, μ(CuKα) = 1.943 mm-1, Dcalc =

1.233 g/cm3, 28497 reflections measured (7.156° ≤ 2Θ ≤ 149.04°), 10338 unique (Rint = 0.0246,

Rsigma = 0.0226) which were used in all calculations. The final R1 was 0.0623 (I >2σ(I)) and wR2

was 0.1867 (all data).

TableS1:Crystal structure data of (2g): (CCDC No.1832862)

Table 1 Crystal data and structure refinement for exp_255-IND8a.

Identification code CCDC No.1832862

Empirical formula C61H49Cl3N4O2

Formula weight 976.39

Temperature/K 93(2)

Crystal system triclinic

NH

O

NH

H3C

CH3

2g

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Space group P-1

a/Å 13.13930(10)

b/Å 14.65600(10)

c/Å 15.47680(10)

α/° 110.2300(10)

β/° 91.2620(10)

γ/° 108.1490(10)

Volume/Å3 2629.10(4)

Z 2

ρcalcg/cm3 1.233

μ/mm-1 1.943

F(000) 1020.0

Crystal size/mm3 0.2 × 0.2 × 0.1

Radiation CuKα (λ = 1.54184)

2Θ range for data collection/° 7.156 to 149.04

Index ranges -15 ≤ h ≤ 16, -18 ≤ k ≤ 18, -19 ≤ l ≤ 13

Reflections collected 28497

Independent reflections 10338 [Rint = 0.0246, Rsigma = 0.0226]

Data/restraints/parameters 10338/0/635

Goodness-of-fit on F2 1.069

Final R indexes [I>=2σ (I)] R1 = 0.0623, wR2 = 0.1847

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Final R indexes [all data] R1 = 0.0645, wR2 = 0.1867

Largest diff. peak/hole / e Å-3 0.49/-0.84

FigureS2 Single crystal X-ray of 2g(CCDC No.1832862). The thermal ellipsoids are drawn at

the 50% probability level. The compound was crystalized with CHCl3.

References:

1. Dolomanov, O.V., Bourhis, L.J., Gildea, R.J, Howard, J.A.K. &Puschmann, H. (2009), J.

Appl. Cryst. 42, 339-341.

2. Sheldrick, G.M. (2015). ActaCryst. A71, 3-8.

3. Sheldrick, G.M. (2015). ActaCryst. C71, 3-8.

NH

O

NH

H3C

CH3

2g