Heterobimetallic Pd-Sn Catalysis: Michael Addition. Reaction with C-, N-, O-, S- Nucleophiles and In-situ. Diagnostics

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1 Supporting Information (SI) Heterobimetallic Pd-Sn Catalysis: Michael Addition Reaction with C-, N-, -, S- Nucleophiles and In-situ Diagnostics Debjit Das, a Sanjay Pratihar a,b and Sujit Roy c * a rganometallics & Catalysis Laboratory, Department of Chemistry, Indian Institute of Technology, Kharagpur , India b Department of Chemical Sciences, Tezpur University, Napaam,784028, Assam, India c rganometallics & Catalysis Laboratory, School of Basic Sciences, Indian Institute of Technology, Bhubaneswar , India sujitroy.chem@gmail.com, sroychem@iitbbs.ac.in Table of Contents: S-1. Initial Kinetic Study S-2. UV-Visible Study S-3. NMR Study for the Interaction of α,β-unsaturated Ketones S-4. RTEP of 3ca and 3cp S-5. DFT Study S-6. Spectra of All Products 1

2 S-1. Initial Kinetic Study A mixture of trimethoxy benzene 2a (0.2 mmol), methyl vinyl ketone 1a (0.02 mmol), and catalyst (1 mol %) in 0.5 ml of CDCl 3 and 10 µl of MeCN was taken at room temperature (30 o C) in a NMR tube. Then the tube was subjected for recording 1 H NMR after different time intervals using triphenyl methane (1 mg) as internal standard. Pseudo-first order rate plots 0.8 k PdCl2 (MeCN) 2 = 3.21 x 10-3 s -1 R = log[(c t - C α )/(C 0 - C α )] Time (min) 2

3 0.5 k SnCl2 = 3.59 x 10-3 s -1 R = log[(c t - C α )/(C 0 - C α )] Time (min) k (CD)PdClSnCl3 = 8.25 x 10-3 s -1 R = log[(c t - C α )/(C 0 - C α )] Time (min) 3

4 -log[(c t - C α )/(C 0 - C α )] k (NBD)PdClSnCl3 = x 10-3 s -1 R = Time (min) -log[(c t - C α )/(C 0 - C α )] k (CHD)PdClSnCl3 = x 10-3 s -1 R = Time (min) 4

5 0.35 k (MeCN)2 PdClSnCl 3 = x 10-3 s -1 R = log[(c t - C α )/(C 0 - C α )] Time (min) S-2. UV-Visible Study 1) A solution of M in MeCN/DCM (1:40) of PdCl 2 (MeCN) 2 was prepared and UV- Visible spectra of this solution was recorded at room temperature. 2) A solution of M in MeCN/DCM (1:40) of PdCl 2 (MeCN) 2 and SnCl 2 (1:1) was prepared and UV-Visible spectra of this solution was recorded at room temperature. 3) To this above solution of PdCl 2 (MeCN) 2 (1 equiv.) and SnCl 2 (1 equiv.), 1 equiv. 1,5- cyclooctadiene was added and UV-Visible spectra of final solution was recorded at room temperature. S-3. NMR Study for the Interaction of α,β-unsaturated Ketones with Pd-Sn To see the initial activation the 13 C spectrum of α,β-unsaturated ketone (1b/1i) was recorded in CDCl 3 /MeCN solvent at room temperature in the absence as well as in the presence of PdCl 2 (MeCN) 2 and SnCl 2 catalytic system. 5

6 Shift in 13 C NMR α,β-unsaturated ketone Catalyst combination Solvent medium Shift of C 1 (ppm) Shift of C 2 (ppm) Shift of C 3 (ppm) (0.05 mmol) PdCl 2 (MeCN) 2 and SnCl 2 (0.05 mmol and 0.05 mmol) CDCl 3 /MeCN (3:1) 800 µl (0.05 mmol) PdCl 2 (MeCN) 2 and SnCl 2 (0.05 mmol and 0.05 mmol) CDCl 3 /MeCN (3:1) 800 µl

7 S-4. RTEP of 3ca (CCDC ) and 3cp (CCDC ) RTEP of 3ca and 3cp with 30% thermal ellipsoids (H atoms are excluded for clarity) 7

8 S-5. DFT Study Electronic energies, electronic states and geometries in Cartesian coordinates (Angstroms), the structures of the following compounds: PdCl 2 (CH 3 CN) 2 E = Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms):

9 SnCl 2 E = Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms): MVK E = Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms):

10 C-1 E = Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms):

11 C-2 E = Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms):

12 C-3 E = Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms):

13

14 (CHD)PdClSnCl 3 E = Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms):

15 (NBD)PdClSnCl 3 E = Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms):

16 (CD)PdClSnCl 3 E = Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms):

17 CHD E = Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms):

18 NBD E = Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms):

19 CD E = Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms):

20 CH 3 CN E = Hartree Electronic state: 1-A Cartesian Coordinates (Angstroms):

21 S-6. Spectra of All Products Me Me Me 3ab 21

22 Me Me Me 3ab 22

23 S 3ac 23

24 S 3ac 24

25 3ad 25

26 3ad 26

27 S 3ae 27

28 S 3ae 28

29 S 3ae 29

30 S 3ae' 30

31 S 3ae' 31

32 S 3ae' 32

33 Br N H 3ag 33

34 Br N H 3ag 34

35 N 3bh 35

36 N 3bh 36

37 N 3bh 37

38 Me Me Me 3ca 38

39 Me Me Me 3ca 39

40 Me Me Me 3ca 40

41 Ph N H 3cf 41

42 Ph N H 3cf 42

43 H Br Me Me 3db 43

44 H Br Me Me 3db 44

45 H Br Me Me 3db 45

46 Ph Ph N H 3ef 46

47 Ph Ph N H 3ef 47

48 HN 3kf 48

49 HN 3kf 49

50 H H Me Me 3la Me 50

51 H H Me Me 3la Me 51

52 CMe 3ai 52

53 CMe 3ai 53

54 CMe 3ai 54

55 Ph 3bk 55

56 Ph 3bk 56

57 Ph Ph 3bl 57

58 Ph Ph 3bl 58

59 Ph Ph 3jj 59

60 Ph Ph 3jj 60

61 Ph Ph 3kl 61

62 Ph Ph 3kl 62

63 S 3cp 63

64 S 3cp 64

65 S 3cp 65

66 S Ph 3ep Ph 66

67 S Ph 3ep Ph 67

68 H S Br 3fq Ph 68

69 H S Br 3fq Ph 69

70 H S Br 3fq Ph 70

71 H S 3go Me 71

72 H S 3go Me 72

73 H S 3go Me 73

74 (CH 2 ) 7 H 3 C S 3gn Me 74

75 (CH 2 ) 7 H 3 C S 3gn Me 75

76 (CH 2 ) 7 H 3 C S 3gn Me 76

77 Me S Cl 3hr 77

78 Me S Cl 3hr 78

79 S Me 3im Me 79

80 S Me 3im Me 80

81 H S Ph 3jo Ph 81

82 H S Ph 3jo Ph 82

83 H S Ph 3jo Ph 83

84 H N 2 N 3au 84

85 H N 2 N 3au 85

86 H N Cl 3av 86

87 87

88 N 3aw 88

89 N 3aw 89

90 N 3ax 90

91 N 3ax 91

92 H N Me 3bt 92

93 H N Me 3bt 93

94 H N Me 3bt 94

95 H N 3cs Ph 95

96 H N 3cs Ph 96

97 H N 3ks 97

98 H N 3ks 98

99 3ay 99

100 3ay 100

101 3az 101

102 3az 102

103 S Ph H H 4a Ph 103

104 S Ph H H 4a Ph 104

105 S Ph H H 4a Ph 105

106 S Ph 5a Ph 106

107 S Ph 5a Ph 107

108 S Ph 5a Ph 108

109 S Ph H H 4b Me 109

110 S Ph H H 4b Me 110

111 S Ph H H 4b Me 111

112 S Ph 5b Me 112

113 S Ph 5b Me 113

114 S Ph 5b Me 114