Supporting information · Sonu Kumar, Rakesh K. Saunthwal, Trapti Aggarwal, Siva K. Reddy Kotla and...

1

Supporting Information Palladium Meets Copper: One-Pot Tandem Synthesis of

Pyrido Fused Heterocycle via Sonogashira conjoined

Electrophilic Cyclization

Sonu Kumar, Rakesh K. Saunthwal, Trapti Aggarwal, Siva K. Reddy Kotla and Akhilesh K.

Verma*

Synthetic Organic Chemistry Research Laboratory, Department of Chemistry,

University of Delhi, Delhi – 110007, India

Email: [email protected]

S. No. Table of contents Page No.

1 X-ray crystallographic studies 2-3

2 References 4-4

3 Copies of 1H NMR, 13C NMR and HRMS 5-104

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

2

X-ray crystallographic studies

.

Figure 1. ORTEP drawing of compound 4b drawn at 50% probability level .

The crystal of compound 4b (CCDC No: 1486060) was generated in CH2Cl2/Hexane. The

intensity data for SON-387 was collected on an Bruker Kappa Apex-CCD diffractometer

equipped with graphite monochromatic Mo-Kα radiation (λ = 0.71073 Ǻ) at 100(2) K1.A

multi-scan correction was applied. The structure was solved by the direct methods using

SIR-92 and refined by full-matrix least-squares refinement techniques on F2 using

SHELXL972. The hydrogen atoms were placed into the calculated positions and included in

the last cycles of the refinement. All calculations were done using Wingx software package3.

3

Table 1. Crystal data collection and structure refinement parameters for 4b Compound 4b Empirical formula Formula weight

C19H14N2 270.32

Temperature 293(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P 21/c A 13.739(5)Å B 5.908(5)Å C 17.319(5)Å α (°) 90.000(5)°

β (°) 91.208(5)°

γ (°) 90.000(5)° Volume 1405.5(14) Å3

Z 4 Density (calculated) 1.278 Mg/m3

Absorption coefficient 0.076 mm-1

F(000) 568 Crystal size 0.20 x 0.19 x 0.17 mm3

Theta range for data collection 3.64 to 25.00° Index ranges -16 ≤ h ≤ 16, -7 ≤ k ≤ 7, -20 ≤ l ≤ 20 Reflections collected 15507 Independent reflections 2465 [R(int) = 0.0390] Completeness to theta = 25.00° 99.8 % Absorption correction Multi-scan Max. and min. transmission 0.9872 and 0.9850 Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 2465 / 0 / 190 Goodness-of-fit on F2 1.038 Final R indices [I>2sigma(I)]a, b R1 = 0.0514, wR2 = 0.1235 R indices (all data) R1 = 0.0823, wR2 = 0.1365 Largest diff. peak and hole 0.168 and -0.149e.Å-3

aR = ∑(║Fo│– │Fc║)/∑│Fo│; bwR = {∑[w(Fo2 ─ Fc

2)2]/∑[w(Fo2)2]}1/2

4

References 1. a) SMART: Bruker Molecular Analysis Research Tool, version 5.618. Bruker Analytical

X-ray System, 2000. b) SAINT-NT, version 6.45, Bruker Analytical X-Ray System, 2003. c)

SHELXTL-NT, version 6.10, Bruker Analytical X-ray System, 2000.

2. G. M. Sheldrick, Acta Cryst., 2008, A64, 112-122.

3. L. J. Farrugia, WinGX Version 1.80.05, An integrated system of Windows Programs for

the Solution, Refinement and Analysis of Single Crystal X-Ray Diffraction Data;

Department of Chemistry, University of Glasgow (1997-2009).

5

Copies of 1H NMR, 13C NMR

and HRMS

6

1H NMR

3-Phenylbenzo[b][1,6]naphthyridine (4a)

7

13C NMR


8

HRMS


+TOF MS: 0.865 to 0.998 min from Sample 1 (TuneSampleID) of 50005.wiffa=3.60979190650730920e-004, t0=-6.01277179989930400e+000 (Turbo Spray)

Max. 3883.3 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400

3600

3800

Inte

nsity

, cou

nts

256.0999

9

1H NMR

3-(p-Tolyl)benzo[b][1,6]naphthyridine (4b)

10

13C NMR


11

HRMS



Max. 3968.1 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400

3600

3800

3968

Inte

nsity

, cou

nts

270.1156

12

1H NMR

3-(4-Butylphenyl)benzo[b][1,6]naphthyridine (4c)

13

13C NMR

3-(4-Butylphenyl)benzo[b][1,6]naphthyridine (4c)

14

HRMS

3-(4-Butylphenyl)benzo[b][1,6]naphthyridine (4c) +TOF MS: 1.514 to 1.597 min from Sample 1 (TuneSampleID) of 017.wiffa=3.43970586567407740e-004, t0=-6.01277179989930400e+000 (Turbo Spray)

Max. 2713.3 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

1600

1700

1800

1900

2000

2100

2200

2300

2400

2500

2600

2700

Inte

nsity

, cou

nts

312.1625

15

1H NMR

3-(Thiophen-3-yl)benzo[b][1,6]naphthyridine (4d)

16

13C NMR


17

HRMS



Max. 4317.0 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400

3600

3800

4000

42004317

Inte

nsity

, cou

nts

262.0565

18

1H NMR

8-Methyl-3-(p-tolyl)benzo[b][1,6]naphthyridine (4e)

19

13C NMR


20

HRMS



Max. 5339.3 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400

3600

3800

4000

4200

4400

4600

4800

5000

52005339

Inte

nsity

, cou

nts

284.1313

21

1H NMR

3-(4-Ethylphenyl)-8-methylbenzo[b][1,6]naphthyridine (4f)

22

13C NMR


23

HRMS



Max. 6265.2 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

6265

Inte

nsity

, cou

nts

298.1471

24

1H NMR

8-Methoxy-3-phenylbenzo[b][1,6]naphthyridine (4g)

25

13C NMR


26

HRMS



Max. 3872.4 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

3400

3600

3800

Inte

nsity

, cou

nts

286.1105

27

1H NMR

3-(4-(t-Butyl)phenyl)-8-methoxybenzo[b][1,6]naphthyridine (4h)

28

13C NMR

3-(4-(t-Butyl)phenyl)-8-methoxybenzo[b][1,6]naphthyridine (4h)

29

HRMS

3-(4-(t-Butyl)phenyl)-8-methoxybenzo[b][1,6]naphthyridine (4h) +TOF MS: 0.681 to 0.798 min from Sample 1 (TuneSampleID) of 005.wiffa=3.60125578360809970e-004, t0=-6.01277179989930400e+000 (Turbo Spray)

Max. 2263.5 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

1600

1700

1800

1900

2000

2100

22002264

Inte

nsity

, cou

nts

342.1732

30

1H NMR

7-(4-(Tert-butyl)phenyl)-1,6-naphthyridine (4i)

31

13C NMR


32

HRMS



Max. 377.8 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

20

40

60

80

100

120

140

160

180

200

220

240

260

280

300

320

340

360

378

Inte

nsity

, cou

nts

262.1470

33

1H NMR

5-Methyl-3-phenyl-5H-pyrido[4,3-b]indole (6a)

34

13C NMR

5-methyl-3-phenyl-5H-pyrido[4,3-b]indole (6a)

35

HRMS

5-methyl-3-phenyl-5H-pyrido[4,3-b]indole (6a)

+TOF MS: 0.698 to 0.798 min from Sample 1 of r10.wiffa=3.40951955889840250e-004, t0=-6.01277179989930400e+000 (Turbo Spray)

Max. 1421.6 counts.

200 220 240 260 280 300 320 340 360 380 400 420 440 460 480m/z, Da

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

Inte

nsity

, cou

nts

258.1156

36

1H NMR

5-Methyl-3-(p-tolyl)-5H-pyrido[4,3-b]indole (6b)

37

13C NMR


38

HRMS


+TOF MS: 1.930 to 2.264 min from Sample 1 of r11.wiffa=3.50086004738864890e-004, t0=-6.01277179989930130e+000 (Turbo Spray)

Max. 1338.4 counts.

120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480m/z, Da

0

50

100

150

200

250

300

350

400

450

500

550

600

650

700

750

800

850

900

950

1000

1050

1100

1150

1200

1250

13001338

Inte

nsity

, cou

nts

272.1313

39

1H NMR

3-(4-Butylphenyl)-5-methyl-5H-pyrido[4,3-b]indole (6c)

40

13C NMR


41

HRMS


+TOF MS: 0.648 to 0.731 min from Sample 1 of 0028.wiffa=3.65464671698700430e-004, t0=-6.01277179989930400e+000 (Turbo Spray)

Max. 556.2 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

50

100

150

200

250

300

350

400

450

500

550

Inte

nsity

, cou

nts

314.1783

42

1H NMR

3-(4-Methoxyphenyl)-5-methyl-5H-pyrido[4,3-b]indole (6d)

43

13C NMR


44

HRMS


45

1H NMR

5-Methyl-3-(thiophen-3-yl)-5H-pyrido[4,3-b]indole (6e)

46

13C NMR


47

HRMS



Max. 343.0 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

20

40

60

80

100

120

140

160

180

200

220

240

260

280

300

320

340

Inte

nsity

, cou

nts

264.0721

48

1H NMR

5-Methyl-3-(4-(trifluoromethyl)phenyl)-5H-pyrido[4,3-b]indole (6f)

49

13C NMR


50

HRMS



Max. 434.3 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

20

40

60

80

100

120

140

160

180

200

220

240

260

280

300

320

340

360

380

400

420434

Inte

nsity

, cou

nts

326.1030

51

1H NMR

5-Methyl-3-phenethyl-5H-pyrido[4,3-b]indole (6g)

52

13C NMR


53

HRMS


54

1H NMR

3-Cyclopropyl-5-methyl-5H-pyrido[4,3-b]indole (6h)

55

13C NMR


56

HRMS


57

1H NMR

3-Butyl-5-methyl-5H-pyrido[4,3-b]indole (6i)

58

13C NMR


59

HRMS


60

1H NMR

3-Phenylisoquinoline (8a)

61

13C NMR


62

HRMS


63

1H NMR

3-(4-Ethylphenyl)isoquinoline (8b)

64

13C NMR


65

HRMS



Max. 1445.0 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

14001445 233.1205

66

1H NMR

3-(3-Methoxyphenyl)isoquinoline (8c)

67

13C NMR


68

HRMS


pa=4.22276555449639430e-004, t0=-5.66662779057200530e+003 (Turbo Spray)

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

50

100

150

200

250

300

350

400

450

500

550

600

650

700

750

800

850

900

950

1000

1050

1100

1150

1200

1250235.0998

69

1H NMR

3-(4-(Trifluoromethyl)phenyl)isoquinoline (8d)

70

13C NMR


71

HRMS



Max. 1642.9 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

1500

16001643 273.0765

72

1H NMR

7-(4-Butylphenyl)-[1,3]dioxolo[4,5-g]isoquinoline (8e)

73

13C NMR


74

HRMS


75

1H NMR

4-([1,3]Dioxolo[4,5-g]isoquinolin-7-yl)-N,N-dimethylaniline (8f)

76

13C NMR


77

HRMS


78

1H NMR

7-(4-(Trifluoromethyl)phenyl)-[1,3]dioxolo[4,5-g]isoquinoline (8g)

79

13C NMR


80

HRMS


81

1H NMR

3-Phenylbenzo[4,5]thieno[2,3-c]pyridine (10a)

82

13C NMR


83

HRMS



Max. 6316.4 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

6316

Inte

nsity

, cou

nts

261.0612

84

1H NMR

3-(p-Tolyl)benzo[4,5]thieno[2,3-c]pyridine (10b)

85

13C NMR


86

HRMS



Max. 5878.2 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

5878

Inte

nsity

, cou

nts

275.0769

87

1H NMR

3-(Thiophen-3-yl)benzo[4,5]thieno[2,3-c]pyridine (10c)

88

13C NMR


89

HRMS



Max. 5751.2 counts.

240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680m/z, Da

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

5751

Inte

nsity

, cou

nts

267.0176

90

1H NMR

3-(4-(Trifluoromethyl)phenyl)benzo[4,5]thieno[2,3-c]pyridine(10d)

91

13C NMR


92

13C NMR



Max. 6056.9 counts.

100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000m/z, Da

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

5500

6000

Inte

nsity

, cou

nts

329.0487

93

1H NMR

3-Phenylbenzofuro[3,2-c]pyridine (12a)

94

13C NMR


95

HRMS


96

1H NMR

3-(4-(Tert-butyl)phenyl)benzofuro[3,2-c]pyridine (12b)

97

13C NMR


98

HRMS


99

1H NMR

3-(3-Methoxyphenyl)benzofuro[3,2-c]pyridine (12c)

100

13C NMR


101

HRMS


102

1HNMR

3-(4-(Trifluoromethoxy)phenyl)benzofuro[3,2-c]pyridine (12d)

103

13C NMR


104

HRMS


Supporting information · Sonu Kumar, Rakesh K. Saunthwal, Trapti Aggarwal, Siva K. Reddy Kotla and...

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Transcript of Supporting information · Sonu Kumar, Rakesh K. Saunthwal, Trapti Aggarwal, Siva K. Reddy Kotla and...