Supporting Information

Transcription

1 Supporting Information One-Pot Access to Benzo[a]carbazoles via Palladium(II)-Catalyzed Hetero- and Carboannulations Moumita Jash, Bimolendu Das, and Chinmay Chowdhury* Organic & dicinal Chemistry Division, Indian Institute of Chemical Biology (CSIR), 4, Raja S. C. Mullick Road, Jadavpur, Kolkata , India Table of Contents 1. Synthesis of ortho-ethynylaniline derivatives S3 (Scheme S1)...S2 2. Preparation of the starting substrates 9 (Scheme S2)...S2 3. Preparation of the Starting Substrates 10 (Scheme S3)...S2 4. ORTEP diagrams of products 5b, 5g and 6f.S3-S4 5. X-Ray crystallographic information of products 5b, 5g and 6f...S4-S7 6. References S8 7. Copies of MR and HRMS Spectra MR Spectra of Compounds 9a-9n...S9-S22 HRMS (EI+) Spectra of 9n.. S23 MR Spectra of Compounds 10a-10n....S24-S37 MR Spectra of Compounds 5a-5n....S38-S51 MR Spectra of Compounds 6a-6n S52-S66 HRMS (EI+) Spectra of 6i..S61 HRMS (EI+) Spectra of 6n.....S67 MR Spectra of Compound S68 S1

2 1. Scheme S1. Synthesis of ortho-ethynylaniline Derivatives S1 R 2 i R Reagents and conditions: (i) I 2, ahco 3, Toluene-H 2 O, rt, 3-5 h, 50-70%; (ii) TMSacetylene, PdCl 2 (PPh 3 ) 2, CuI, Et 3, rt, 1-6 h, 82-98%; (iii) K 2 CO 3, OH, rt, 2 h, 69-81% I 2 ii, iii R S Scheme S2. Preparation of the Starting Substrates 9 R 1 R 3 R 4 C i R 1 C R 4 R 4 R 3 C R 2 R 1 ii R 3 R 2 S1 2 R 2 I S2 2 9 PG PG = /s/ms Reagents and conditions: (i) PdCl 2 (PPh 3 ) 2, CuI, Et 3, rt, h, 82-98%; (ii) Cl/sCl/MsCl, pyridine, DCM, 0 ºC-rt, h, 62-94% 3. Scheme S3. Preparation of the Starting Substrates 10 R 3 R 3 O R 1 R 2 i R 1 2 I S1 (R 3 =H/) O S3 2 ii R 2 O R 3 R 3 R 2 OHC R 2 R 1 S4 iii R 1 10 Reagents and conditions: (i) PdCl 2 (PPh 3 ) 2, CuI, Et 3, rt, h, 56-92%; (ii) Cl, pyridine, DCM, 0 o C-rt, h, 60-86%; (iii) p-oh, dry acetone, rt, 3-6 h, 47-76% S2

3 4. X-ray diffraction analysis of products 5b, 5g and 6f: Figure S1. ORTEP Diagram (thermal ellipsoid plot) of Product 5b (drawn at 50% probability level) Figure S2. ORTEP Diagram (thermal ellipsoid plot) of Product 5g (drawn at 50% probability level) S3

4 Figure S3. ORTEP Diagram (thermal ellipsoid plot) of Product 6f (drawn at 50% probability level) 5. X-Ray crystallographic information of products 5b, 5g and 6f: Single crystal of products 5b, 5g and 6f were obtained through slow evaporation (at room temperature) of a solution in dichloromethane-petroleum ether. A single crystal of 5b, 5g and 6f were attached to a glass fiber with epoxy glue and transferred to a X-ray diffractometer, equipped with a graphite-monochromator. Diffraction data of products 5b, 5g and 6f were measured with MoKα radiation (λ = Å) at 293 K. The structure was solved by direct methods using the SHELXS-97 program. 1 Refinements were carried out with a full matrix least squares method against F 2 using SHELXL The non-hydrogen atoms were refined with anisotropic thermal parameters. The hydrogen atoms were included in geometric positions and given thermal parameters equivalent to 1.2 times those of the atom to which they were attached. The important crystal data of product 5b, 5g and 6f are given below: S4

5 Table S1: Important crystal data of product 5b Empirical formula C 24 H 20 2 O 2 S Formula weight Temperature 293 K Wavelength Crystal system Monoclinic Space group P 1 21/c 1 Unit cell dimensions a = 8.462(2) Å α = o b = (5) Å β = (15) c = (4) Å γ = o Volume (10) Å 3 Z 4 Density (calculated) g/cm 3 Absorption coefficient (Mu) mm -1 F(000) Theta range for data collection Index ranges Reflection collected o to o -10<=h<=9, -19<=k<=20, -18<=l<=18 Independent reflections 4384 [R(int) = ] Completeness to theta= o 98.3 % Absorption correction multi-scan Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4384 /0/266 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole & e.a -3 The crystal data of product 5b has already been deposited at Cambridge Crystallographic Data Centre. The CCDC reference number is S5

6 Table S2: Important crystal data of product 5g Empirical formula C 25 H 22 2 O 4 S Formula weight Temperature 293 K Wavelength Crystal system Tetragonal Space group I 41/a Unit cell dimensions Volume (7) Å 3 Z 16 Density (calculated) g/cm 3 Absorption coefficient (Mu) mm -1 F(000) Theta range for data collection Index ranges Reflection collected a = (7)Å α = o b = (7) Å β = o c = (7) Å γ = o o to o -36<=h<=36, -36<=k<=36, -11<=l<=14 Independent reflections 5025 [R(int) = ] Completeness to theta = o 99.4 % Absorption correction multi-scan Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5025/0/293 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole & e.A -3 The crystal data of product 5g has already been deposited at Cambridge Crystallographic Data Centre. The CCDC reference number is S6

7 Table S3: Important crystal data of product 6f Empirical formula Formula weight Temperature C 23 H 16 FO 2 S 293 K Wavelength Crystal system Monoclinic Space group P 1 21/c 1 Unit cell dimensions Volume (2) Å 3 Z 4 Density (calculated) g/cm 3 Absorption coefficient (Mu) mm -1 F(000) Theta range for data collection Index ranges Reflection collected a = (5) Å α = o b = (10) Å β = o (3) c = (9) Å γ = o o to o -8<=h<=10, -20<=k<=20, -19<=l<=18 Independent reflections 4260 [R(int) = ] Completeness to theta = o 99.4 % Absorption correction multi-scan Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4260 /0/254 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole & e.a -3 The crystal data of product 6f has already been deposited at Cambridge Crystallographic Data Centre. The CCDC reference number is S7

8 6. References: 1. Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, Sheldrick, G. M. SHELX - 97, Program for Crystallography Refinement, University of Gottingen: Gottingen, Germany, S8

9 7. Copies of MR and HRMS Spectra 1 H MR (300MHz) Spectrum of 9a: C 9a 13 C MR (75 MHz) Spectrum of 9a: C 9a S9

10 1 H MR (300MHz) Spectrum of 9b: C H 3 C 9b 13 C MR (75 MHz) Spectrum of 9b: C H 3 C 9b S10

11 1 H MR (300 MHz) Spectrum of 9c: C O 9c 13 C MR (75 MHz) Spectrum of 9c: C O 9c S11

12 1 H MR (300 MHz) Spectrum of 9d: C Br 9d 13 C MR (75 MHz) Spectrum of 9d: C Br 9d S12

13 1 H MR (300 MHz) Spectrum of 9e: C F 9e 13 C MR (75 MHz) Spectrum of 9e: C F 9e S13

14 1 H MR (300 MHz) Spectrum of 9f: C F 3 C 9f 13 C MR (75 MHz) Spectrum of 9f: C F 3 C 9f S14

15 1 H MR (300 MHz) Spectrum of 9g: C O O 9g 13 C MR (75 MHz) Spectrum of 9g: C O O 9g S15

16 1 H MR (300 MHz) Spectrum of 9h: C O F 3 C O 9h 13 C MR (75 MHz) Spectrum of 9h: C O F 3 C O 9h S16

17 1 H MR (300 MHz) Spectrum of 9i: C CO 2 9i 13 C MR (75 MHz) Spectrum of 9i: C CO 2 9i S17

18 1 H MR (300 MHz) Spectrum of 9j: C CF 3 9j 13 C MR (75 MHz) Spectrum of 9j: C CF 3 9j S18

19 1 H MR (300 MHz) Spectrum of 9k: C Ms 9k 13 C MR (75 MHz) Spectrum of 9k: C Ms 9k S19

20 1 H MR (300 MHz) Spectrum of 9l: C s 9l 13 C MR (75 MHz) Spectrum of 9l: C s 9l S20

21 1 H MR (300 MHz) Spectrum of 9m: C O s 9m 13 C MR (75 MHz) Spectrum of 9m: C O s 9m S21

22 1 H MR (300 MHz) Spectrum of 9n: C 9n 13 C MR (75 MHz) Spectrum of 9n: C 9n S22

23 DEPT-135 (75 MHz) Spectrum of 9n: C 9n HRMS (EI+) Spectra of 9n: S23

24 MR Spectra of Compounds 10a-n: 1 H MR (300 MHz) Spectrum of 10a: OHC 10a 13 C MR (75 MHz) Spectrum of 10a: OHC 10a S24

25 1 H MR (300 MHz) Spectrum of 10b: OHC 10b 13 C MR (75 MHz) Spectrum of 10b: OHC 10b S25

26 1 H MR (300 MHz) Spectrum of 10c: OHC O 10c 13 C MR (75 MHz) Spectrum of 10c: OHC O 10c S26

27 1 H MR (300 MHz) Spectrum of 10d: OHC Br 10d 13 C MR (75 MHz) Spectrum of 10d: OHC Br 10d S27

28 1 H MR (300 MHz) Spectrum of 10e: OHC Cl OHC Cl 10e 13 C MR (75 MHz) Spectrum of 10e: OHC Cl 10e S28

29 1 H MR (300 MHz) Spectrum of 10f: OHC F 10f 13 C MR (75 MHz) Spectrum of 10f: OHC F 10f S29

30 1 H MR (300 MHz) Spectrum of 10g: OHC O 2 C 10g 13 C MR (75 MHz) Spectrum of 10g: OHC O 2 C 10g S30

31 1 H MR (300 MHz) Spectrum of 10h: OHC 10h 13 C MR (75 MHz) Spectrum of 10h: OHC 10h S31

32 1 H MR (300 MHz) Spectrum of 10i: OHC 10i 13 C MR (75 MHz) Spectrum of 10i: OHC 10i S32

33 1 H MR (300 MHz) Spectrum of 10j: OHC Br 10j 13 C MR (75 MHz) Spectrum of 10j: OHC Br 10j S33

34 1 H MR (300 MHz) Spectrum of 10k: OHC F 10k 13 C MR (75 MHz) Spectrum of 10k: OHC F 10k S34

35 1 H MR (300 MHz) Spectrum of 10l: OHC 10l 13 C MR (75 MHz) Spectrum of 10l: OHC 10l S35

36 1 H MR (300 MHz) Spectrum of 10m: OHC 10m 13 C MR (75 MHz) Spectrum of 10m: OHC 10m S36

37 1 H MR (300 MHz) Spectrum of 10n: OHC Br 10n 13 C MR (75 MHz) Spectrum of 10n: OHC Br 10n S37

38 MR Spectra of Compounds 5a-n 1 H MR (300 MHz) Spectrum of 5a: H 2 5a 13 C MR (75 MHz) Spectrum of 5a: H 2 5a S38

39 1 H MR (300 MHz) Spectrum of 5b: H 2 5b 13 C MR (75 MHz) Spectrum of 5b: H 2 5b S39

40 1 H MR (600 MHz) Spectrum of 5c: H 2 O 5c 13 C MR (150 MHz) Spectrum of 5c: H 2 O 5c S40

41 1 H MR (600 MHz) Spectrum of 5d: H 2 Br 5d 13 C MR (150 MHz) Spectrum of 5d: H 2 Br 5d S41

42 1 H MR (600 MHz) Spectrum of 5e: H 2 F 5e 13 C MR (150 MHz) Spectrum of 5e: H 2 F 5e S42

43 1 H MR (300 MHz) Spectrum of 5f: H 2 F 3 C 5f 13 C MR (150 MHz) Spectrum of 5f: H 2 F 3 C 5f S43

44 1 H MR (300 MHz) Spectrum of 5g: H 2 O 5g O 13 C MR (150 MHz) Spectrum of 5g: H 2 O 5g O S44

45 1 H MR (600 MHz) Spectrum of 5h: H 2 F 3 C O 5h O 13 C MR (150 MHz) Spectrum of 5h: H 2 F 3 C O 5h O S45

46 1 H MR (600 MHz) Spectrum of 5i: H 2 5i CO 2 13 C MR (150 MHz) Spectrum of 5i: H 2 5i CO 2 S46

47 1 H MR (600 MHz) Spectrum of 5j: H 2 5j CF 3 13 C MR (150 MHz) Spectrum of 5j: H 2 5j CF 3 S47

48 1 H MR (300 MHz) Spectrum of 5k: H 2 Ms 5k 13 C MR (75 MHz) Spectrum of 5k: H 2 Ms 5k S48

49 1 H MR (300 MHz) Spectrum of 5l: H 2 s 5l 13 C MR (75 MHz) Spectrum of 5l: H 2 s 5l S49

50 1 H MR (300 MHz) Spectrum of 5m: H 2 O s 5m 13 C MR (150 MHz) Spectrum of 5m: H 2 O s 5m S50

51 1 H MR (600 MHz) Spectrum of 5n: H 2 5n 13 C MR (150 MHz) Spectrum of 5n: H 2 5n S51

52 MR Spectra of Compounds 6a-n: 1 H MR (600 MHz) Spectrum of 6a: 6a 13 C MR (150 MHz) Spectrum of 6a: 6a S52

53 1 H MR (600 MHz) Spectrum of 6b: H 3 C 6b 13 C MR (150 MHz) Spectrum of 6b: H 3 C 6b S53

54 1 H MR (600 MHz) Spectrum of 6c: O 6c 13 C MR (150 MHz) Spectrum of 6c: O 6c S54

55 1 H MR (600 MHz) Spectrum of 6d: Br 6d 13 C MR (150 MHz) Spectrum of 6d: Br 6d S55

56 1 H MR (600 MHz) Spectrum of 6e: Cl 6e 13 C MR (150 MHz) Spectrum of 6e: Cl 6e S56

57 1 H MR (600 MHz) Spectrum of 6f: F 6f 13 C MR (150 MHz) Spectrum of 6f: F 6f S57

58 1 H MR (600 MHz) Spectrum of 6g: O 2 C 6g 13 C MR (150 MHz) Spectrum of 6g: O 2 C 6g S58

59 1 H MR (300 MHz) Spectrum of 6h: 6h 13 C MR (75 MHz) Spectrum of 6h: 6h S59

60 1 H MR (600 MHz) Spectrum of 6i: 6i 13 C MR (150 MHz) Spectrum of 6i: 6i S60

61 HRMS (EI+) Spectra of 6i: S61

62 1 H MR (600 MHz) Spectrum of 6j: Br 6j 13 C MR (150 MHz) Spectrum of 6j: Br 6j S62

63 1 H MR (300 MHz) Spectrum of 6k: 6k F 13 C MR (75 MHz) Spectrum of 6k: 6k F S63

64 1 H MR (600 MHz) Spectrum of 6l: 6l 13 C MR (150 MHz) Spectrum of 6l: 6l S64

65 1 H MR (600 MHz) Spectrum of 6m: 6m 13 C MR (150 MHz) Spectrum of 6m: 6m S65

66 1 H MR (600 MHz) Spectrum of 6n: Br 6n 13 C MR (150 MHz) Spectrum of 6n: Br 6n S66

67 HRMS (EI+) Spectra of 6n: S67

68 MR Spectra of Compounds 11: 1 H MR (600 MHz) Spectrum of 11: H 2 11 H 13 C MR (150 MHz) Spectrum of 11: H 2 11 H S68