electronic supplementary information · 1 electronic supplementary information efficient asymmetric...

1

Electronic Supplementary Information

Efficient asymmetric synthesis of N-protected--

aryloxyamino acids via regioselective ring

opening of serine sulfamidate carboxylic acid

Rajesh Malhotra,a Tushar K. Dey,

a,b Swarup Dutta,

b Sourav Basu*

b and Saumen Hajra*

c

a Guru Jambheshwar University of Science and Technology, Hisar, Haryana 125001, India.

b TCG Life Sciences Ltd, Saltlake, Kolkata 700091, India, and Department of Chemistry,

c Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302, India;

sourav@chembiotek.com; shajra@chem.iitkgp.ernet.in

Contents

NMR Spectra, LC-MS and HPLC Chromatogram

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2014

2

NMR Spectra, LC-MS and Chromatogram

1H NMR spectrum (400 MHz, CDCl3) of (S)-4-benzyl-3-tert-butyl 1,2,3-oxathiazolidine-3,4-

dicarboxylate 2,2-dioxide 1.

13

C NMR spectrum (100 MHz, CDCl3) of (S)-4-benzyl-3-tert-butyl 1,2,3-oxathiazolidine-

3,4-dicarboxylate 2,2-dioxide 1.

3

APT NMR spectrum (100MHz, CDCl3) of (S)-4-benzyl-3-tert-butyl 1,2,3-oxathiazolidine-

3,4-dicarboxylate 2,2-dioxide 1.

IR of ((S)-4-benzyl-3-tert-butyl 1,2,3-oxathiazolidine-3,4-dicarboxylate 2,2-dioxide 1.

4

LCMS of ((S)-4-benzyl-3-tert-butyl 1,2,3-oxathiazolidine-3,4-dicarboxylate 2,2-dioxide 1

5

1H NMR spectrum (400 MHz, acetone-d6) of compound 4

1H NMR spectrum (400 MHz, MeOH-d4) of compound 4

6

13

C NMR spectrum (100 MHz, MeOH-d4) of compound 4

APT NMR spectrum (100 MHz, MeOH-d4) of compound 4

7

LCMS of compound 4

8

1H NMR spectrum (400 MHz, DMSO-d6) of compound 2ʹ(R = H)

9

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6a

13C NMR spectrum (100 MHz, DMSO-d6) of compound 6a

10

APT NMR spectrum (100 MHz, DMSO-d6) of compound 6a

11

LCMS of compound 6a

12

Chiral HPLC of 6a (L-isomer)

13

Chiral HPLC of 6a (D-isomer)

14

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6b

15

13

C NMR spectrum (100 MHz, DMSO-d6) of compound 6b

APT NMR spectrum (100 MHz, DMSO-d6) of compound 6b

16

LCMS of compound 6b

17

Chiral HPLC of 6b (L-isomer)

18

Chiral HPLC of 6b (D-isomer)

19

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6c

13

C NMR spectrum (100 MHz, DMSO-d6) of compound 6c

20

APT NMR spectrum (100 MHz, DMSO-d6) of compound 6c

21

LCMS of compound 6c

22

Chiral HPLC of 6c (L-isomer)

23

Chiral HPLC of 6c (D-isomer)

24

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6d

25

13

C NMR spectrum (100 MHz, DMSO-d6) of compound 6d

APT NMR spectrum (100 MHz, DMSO-d6) of compound 6d

26

LCMS spectrum of compound 6d

27

Chiral HPLC of 6d (L-isomer)

28

Chiral HPLC of 6d (D-isomer)

29

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6e

30

13

C NMR spectrum (100 MHz, DMSO-d6) of compound 6e

31

APT NMR spectrum (100 MHz, DMSO-d6) of compound 6e

LCMS spectrum of compound 6e

32

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6f

13

C NMR spectrum (100 MHz, DMSO-d6) of compound 6f

33

APT NMR spectrum (100 MHz, DMSO-d6) of compound 6f

34

LCMS spectrum of compound 6f

35

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6g

36

13C NMR spectrum (100 MHz, DMSO-d6) of compound 6g

APT NMR spectrum (100 MHz, DMSO-d6) of compound 6g

37

LCMS spectrum of compound 6g

38

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6h

13

C NMR spectrum (100 MHz, DMSO-d6) of compound 6h

39

APT NMR spectrum (100 MHz, DMSO-d6) of compound 6h

40

LCMS spectrum of compound 6h

41

Chiral HPLC of 6h (L-isomer)

42

Chiral HPLC of 6h (D-isomer)

43

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6i

44

13

C NMR spectrum (100 MHz, DMSO-d6) of compound 6i

APT NMR spectrum (100 MHz, DMSO-d6) of compound 6i

45

LCMS spectrum of compound 6i

46

Chiral HPLC of 6i (L-isomer)

47

Chiral HPLC of 6i (D-isomer)

48

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6j

49

13

C NMR spectrum (100 MHz, DMSO-d6) of compound 6j

APT NMR spectrum (100 MHz, DMSO-d6) of compound 6j

50

LCMS spectrum of compound 6j

51

52

Chiral HPLC of 6j (L-isomer)

53

Chiral HPLC of 6j (D-isomer)

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6k

54

13C NMR spectrum (100MHz, DMSO-d6) of compound 6k

APT NMR spectrum (100 MHz, DMSO-d6) of compound 6k

55

LCMS spectrum of compound 6k

56

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6l

57

13C NMR spectrum (100 MHz, DMSO-d6) of compound 6l

APT NMR spectrum (100 MHz, DMSO-d6) of compound 6l

58

LCMS spectrum of compound 6l

59

Chiral HPLC of 6l (L-isomer)

60

Chiral HPLC of 6l (D-isomer)

61

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6m

62

13

C NMR spectrum (100 MHz, DMSO-d6) of compound 6m

APT

NMR spectrum (100 MHz, DMSO-d6) of compound 6m

63

LCMS spectrum of compound 6m

64

Chiral HPLC of 6m (L-isomer)

65

Chiral HPLC of 6m (D-isomer)

66

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6n

67

13

C NMR spectrum (100 MHz, DMSO-d6) of compound 6n

68

APT NMR spectrum (100 MHz, DMSO-d6) of compound 6n

LCMS spectrum of compound 6n

69

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6o

70

13C NMR spectrum (100 MHz, DMSO-d6) of compound 6o

APT NMR spectrum (100MHz, DMSO-d6) of compound 6o

71

LCMS spectrum of compound 6o

72

Chiral HPLC of 6o (L-isomer)

73

Chiral HPLC of 6o (D-isomer)

74

1H NMR spectrum (400 MHz, DMSO-d6) of compound 6p

75

13

C NMR spectrum (100MHz, DMSO-d6) of compound 6p

APT NMR spectrum (100 MHz, DMSO-d6) of compound 6p

76

LCMS spectrum of compound 6p

77

1H NMR (400 MHz, CDCl3) of compound 8

78

13C NMR (100 MHz, CDCl3) of compound 8

APT (100 MHz, CDCl3) of compound 8

79

1H NMR (400 MHz, CDCl3) of sulfamidate 9

1H NMR (400MHz, DMSO-d6) of sulfamidate 9

80

LCMS of sulfamidate 9

81

13

C NMR (100 MHz, CDCl3) of sulfamidate 9

APT (100 MHz, CDCl3) of sulfamidate 9

82

1H NMR (400 MHz, DMSO-d6) of compound 10c

83

13C NMR (100 MHz, DMSO-d6) of compound 10c

LCMS of compound 10c

84

1H NMR (400 MHz, DMSO-d6) of compound 10d

85

LCMS of compound 10d

86

13

C NMR (100 MHz, DMSO-d6) of compound 10d

APT (100 MHz, DMSO-d6) of compound 10d

87

Chiral HPLC of L-Isomer of compound 10d

88

Chiral HPLC of D-Isomer of compound 10d

89

1H NMR (400 MHz, DMSO-d6) of compound 10f

90

LCMS of compound 10f

91

13

C NMR (100 MHz, DMSO-d6) of compound 10f

APT (100 MHz, DMSO-d6) of compound 10f

92

1H NMR (400 MHz, DMSO-d6) of compound 10g

93

LCMS of compound 10g

94

13

C NMR (100 MHz, DMSO- d6 + TFA) of compound 10g

95

1H NMR (400 MHz, DMSO-d6) of compound 10j

96

LCMS of compound 10j

97

13

C NMR (100 MHz, DMSO-d6) of compound 10j

APT (100 MHz, DMSO-d6) of compound 10j

98

Chiral HPLC of L-isomer of 10j

99

Chiral HPLC of D-Isomer of 10j

100

1H NMR (400 MHz, DMSO-d6) of compound 10m

101

LCMS of compound 10m

102

13

C NMR (100 MHz, DMSO-d6) of compound 10m

APT (100 MHz, DMSO-d6) of compound 10m

103

1H NMR (400 MHz, DMSO-d6) of compound 10o

104

LCMS of compound 10o

105

13

C NMR (100 MHz, DMSO-d6) of compound 10o

APT (100 MHz, DMSO-d6) of compound 10o

106

1H NMR (400 MHz, MeOD) of compound 10q

107

LCMS of compound 10q

108

13

C NMR (100 MHz, MeOD + 3 drop CDCl3) of compound 10q

APT (100 MHz, MeOD + 3 drop CDCl3) of compound 10q

109

Chiral HPLC of L-isomer of 10q

110

Chiral HPLC of D-isomer of 10q