Supplementary Information

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1 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2017 Supplementary Information Intermolecular Sulfenoamination of Alkenes with Sulfonylamides and N-Sulfanylsuccinimides for the Synthesis of -Sulfonylamino sulfides and Dihydrobenzothiazines Tao Liu, a Jun Tian, b Wen-Chao Gao,* a Hong-Hong Chang, a Qiang Liu,* a Xing Li, a and Wen-Long Wei a a College of Chemistry and Chemical Engineering, and b College of Data Science, Taiyuan University of Technology, Taiyuan , P. R. China gaowenchao@tyut.edu.cn liuqiang@tyut.edu.cn Table of contents Table S1. Optimization of reaction conditions for the synthesis of 11a...S2 MS on Mechanism Study...S3 Ring Opening of Phenyl N-tosylaziridine with Thiocresol...S5 Crystal Structure of 4m and the Corresponding Data...S5 Crystal Structure of 9 and the Corresponding Data...S6 NMR Spectra of Products...S8 S1

2 Table S1. Optimization of reaction conditions for the synthesis of 11a a Entry Conditions Yield (%) b 1 1) TfOH (20 mol %), CH2Cl2 (1 ml), 60 o C; 0 2) Pd(OAc)2 (20 mol %), BINAP (40 mol %), K2CO3 (2.5 eq), Toluene, 110 o C 2 1) TfOH (20 mol %), Toluene (1 ml), 60 o C; 0 2) Pd(OAc)2 (20 mol %), BINAP (40 mol %), K2CO3 (2.5 eq), Toluene, 110 o C 3 1) TfOH (20 mol %), CH2Cl2 (1 ml), 60 o C; 0 2) CuI (10 mol %), ethylenediamine (20 mol %), K2CO3 (2.0 eq), 1,4-Dioxane, 100 o C 4 1) TfOH (20 mol %), CH2Cl2 (1 ml), 60 o C; 27 2) Cu (1.1 eq), DMF (1 ml), N2, 120 o C 5 1) TfOH (20 mol %), DCE (1 ml), 60 o C; 0 2) Cu (1.1 eq), DMF (1 ml), N2, 120 o C 6 1) TfOH (20 mol %), Toluene (1 ml), 60 o C; 66 2) Cu (1.1 eq), DMF (1 ml), N2, 120 o C 7 1) TfOH (20 mol %), Toluene (0.5 ml), 60 o C; 72 2) Cu (1.1 eq), DMF (1 ml), N2, 120 o C 8 1) BF3 Et2O (20 mol %), Toluene (1 ml), 60 o C; 2) Cu (1.1 eq), DMF (1 ml), N2, 120 o C 54 a Reaction conditions: 1a (0.2 mmol), 2e (0.3 mmol), and 3a (0.22 mmol) was subjected to the indicated conditions. b Isolated yield. S2

3 MS on Mechanism Study Mass spectroscopy (MALDI) for the reaction of 1a with 2a S3

4 Mass spectroscopy (MALDI) for the reaction of 1j with 2a O O N S BF 3 Et 2 O(20mol%) + CH Ph Ph 2 Cl 2,rt O min 1j 2a Me O Ph Me S Ph Chemical Formula: C 22 H 19 OS + Exact Mass: S4

5 Synthesis of -Sulfonamino Sulfides through Ring Opening of Phenyl N-tosylaziridine with p-thiocresol Ph Ts N p-thiocresol (1.1 equiv) K 2 CO 3 (1.1 equiv) NHTs STol STol + Ph Ph toluene, reflux, 6 h 10 4a yield: 90% ratio = 1: a' NHTs Crystal Structure of 4m and the Corresponding Data ORTEP drawing of 4m (CCDC ); thermal ellipsoids are set at a 30% probability level Crystal Structure Information of 4m Crystal data Chemical formula C29H27ClNO3S2 Mr Crystal system, space group Monoclinic, P21/c Temperature (K) 290 a, b, c (Å) (4), (8), (4) β ( ) (1) V (Å 3 ) (17) Z 4 Radiation type Mo Kα S5

6 µ (mm 1 ) 0.33 Crystal size (mm) Data collection Diffractometer Absorption correction No. of measured, independent and observed [I > 2σ(I)] reflections Bruker APEX-II CCD diffractometer Multi-scan SADABS 25814, 6640, 4696 Rint (sin θ/λ)max (Å 1 ) Refinement R[F 2 > 2σ(F 2 )], wr(f 2 ), S 0.061, 0.157, 1.06 No. of reflections 6640 No. of parameters 327 H-atom treatment H-atom parameters constrained Δρmax, Δρmin (e Å 3 ) 0.32, 0.51 Crystal Structure of 9 and the Corresponding Data ORTEP drawing of 9 (CCDC ); thermal ellipsoids are set at a 30% probability level S6

7 Crystal Structure Information of 9 Crystal data Chemical formula C19H23NO2S2 Mr Crystal system, space group Monoclinic, P21/c Temperature (K) 284 a, b, c (Å) (5), (8), (5) β ( ) (1) V (Å 3 ) (15) Z 4 Radiation type Mo Kα µ (mm 1 ) 0.29 Crystal size (mm) Data collection Diffractometer Absorption correction No. of measured, independent and observed [I > 2σ(I)] reflections Bruker APEX-II CCD diffractometer Multi-scan SADABS 18068, 4730, 3414 Rint (sin θ/λ)max (Å 1) Refinement R[F 2 > 2σ(F 2 )], wr(f 2 ), S 0.053, 0.163, 1.01 No. of reflections 4730 No. of parameters 219 H-atom treatment H-atom parameters constrained Δρmax, Δρmin (e Å 3 ) 0.50, 0.42 S7

8 NMR Spectra of Products 4a S8

9 4a S9

10 4b S10

11 4b S11

12 4c S12

13 4c S13

14 4d S14

15 4d S15

16 4e S16

17 4e S17

18 4f S18

19 4f S19

20 4g S20

21 4g S21

22 4h S22

23 4h S23

24 4i S24

25 4i S25

26 4j S26

27 4j S27

28 4k S28

29 4k S29

30 4l S30

31 4l S31

32 4m S32

33 4m S33

34 4n S34

35 4n S35

36 4o S36

37 4o S37

38 4pa+4pb S38

39 4pa S39

40 4pa S40

41 4q S41

42 4q S42

43 4r S43

44 4r S44

45 4s S45

46 4s S46

47 4s S47

48 8 S48

49 8 S49

50 9 S50

51 9 S51

52 4t S52

53 4t S53

54 4u S54

55 4u S55

56 4v S56

57 4v S57

58 4w S58

59 4w S59

60 4x S60

61 4x S61

62 4y S62

63 4y S63

64 4z S64

65 4z S65

66 4aa S66

67 4aa S67

68 4bb S68

69 4bb S69

70 S70

71 11a S71

72 11a S72

73 11b S73

74 11b S74

75 11c S75

76 11c S76

77 11d S77

78 11d S78

79 11e S79

80 11e S80

81 11f S81

82 11f S82

83 11g S83

84 11g S84

85 13 S85

86 13 S86

87 14 S87

88 14 S88