supporting information - the royal society of chemistry supporting information enantioselective...

1

Supporting Information

Enantioselective total Syntheses and determination of absolute

configuration of marine toxins, oxazinins.

Dattatraya H. Dethe* and Alok Ranjan

Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur – 208016, India

Tel: + 91-512-2596537, Fax: + 91-512-2597436.

Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013

2

Table of Contents:

NMR of Compound 15, 17, 18: ........................................................................................3

NMR of Compound 19, 20, 22: ........................................................................................7

NMR of Compound 24, 26, 27: ......................................................................................12

NMR of Compound 21, 23, 25: ......................................................................................22

NMR of Compound 13, 28: ............................................................................................27

NMR of Compound 30: ..................................................................................................33

NMR of Compound 34: ..................................................................................................47

NMR of Compound 35 : .................................................................................................48

NMR of compound 10: ...................................................................................................21

NMR of Compound 11: ..................................................................................................18

NMR of Compound 7: ....................................................................................................35

NMR of Compound 9: ....................................................................................................31

NMR of Compound 5: ....................................................................................................40

NMR of Compound 6 :....................................................................................................44

NMR of Compound 1: ....................................................................................................50

NMR of Compound 2: ....................................................................................................53

NMR of Compound 4: ....................................................................................................51

CD Spectra of Oxazinin-5: .............................................................................................55

CD Spectra of Preoxazinin-7: ........................................................................................56

CD Spectra of Oxazinin-6: .............................................................................................57

HPLC of Compound 21: .............................................................................................59

NMR Spectrum:


3

30 May 2011Alok

Z:\AV200\OCT_09~1\data\ADMINI~1\nmr\MOE13D~1\1\pdata\1\1r

Acquisition Time (sec) 7.9167 Comment Alok Date 19/10/2009 15:38:24 Frequency (MHz) 200.13

Nucleus 1H Original Points Count 32768 Points Count 32768 Sweep Width (Hz) 4139.07

Temperature (grad C) 0.000

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0

6.89 3.062.02 2.00 1.960.97 0.96

Chloroform-d

1.30

1.33

1.37

4.20

4.24

4.27

4.31

5.10

6.27

6.35

6.95

7.00

7.26

7.36

7.37

7.40

7.41

7.42

7.45

7.49

7.50

7.60

7.68

30 May 2011Alok

Z:\AV200\OCT_09~1\data\ADMINI~1\nmr\WEFC94~1\1\pdata\1\1r


Nucleus 13C Original Points Count 32768 Points Count 32768 Sweep Width (Hz) 11990.41


190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

Chloroform-d14

.33

60.3

2

70.0

6

76.3

677

.00

77.6

3

115.

1811

5.87

127.

4412

8.13

128.

6412

9.68

136.

45

144.

17

160.

47

167.

31


4

Sat2av2#029.001.001.1r.esp

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

3.000.850.913.011.012.052.066.95

0.00

1.22

1.25

1.29

1.65

2.73

2.76

3.15

3.18

4.19

4.23

4.26

4.29

4.30

4.31

4.33

4.91

4.93

4.94

4.96

5.06

6.95

6.99

7.25

7.31

7.34

7.35

7.37

7.38

7.41

7.44

30 May 2011Alok

Z:\AV200\OCT_09~1\data\ADMINI~1\nmr\WEFC94~1\2\pdata\1\1r




190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

14.3

9

60.3

8

70.0

9

115.

2111

5.90

127.

5012

8.19

128.

7012

9.74

144.

23


5

Wed3av2#064.001.001.1r.esp

192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)

14.0

6

62.1

1

69.9

6

74.1

874

.69

76.3

777

.00

77.6

4

114.

73

127.

4112

7.61

127.

9412

8.55

132.

31

136.

85

158.

56

172.

74

Wed3av2#064.002.001.1r.esp

184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)

14.1

3

62.1

9

70.0

374

.25

74.7

6

114.

80

127.

4812

7.68

128.

0312

8.64

OBn

CO2Et

OHHO

(CDCl3, 25 °C)17

OBn

CO2Et

OHHO

(CDCl3, 25 °C)17


6

Wed3av2#027.001.001.1r.esp

10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)

3.101.092.001.041.820.951.961.984.821.941.91

1.14

1.17

1.21

2.59

4.10

4.14

4.17

4.21

4.94

4.96

4.99

5.13

5.15

6.78

6.82

7.11

7.15

7.26

7.36

7.37

7.39

7.40

7.41

7.42

7.43

7.81

7.86

7.87

8.19

8.23

8.24

Sat3av2#058.002.001.1r.esp


13.8

4

62.4

7

69.9

273

.04

76.3

677

.00

77.6

3

82.4

2

114.

69

124.

0412

7.41

127.

5312

8.10

128.

5912

9.09

129.

5213

6.39

141.

37

150.

45

158.

93

166.

42

(CDCl3, 25 °C)18

OBn

CO2Et

ONsHO

(CDCl3, 25 °C)18

OBn

CO2Et

ONsHO


7

Sat3av2#058.001.001.1r.esp


13.9

4

62.5

8

70.0

1

73.1

4

82.5

2

114.

78

124.

1412

7.51

127.

6312

8.21

128.

6912

9.19

Sat4av2#004.001.001.1r.esp


3.041.280.870.911.950.981.981.977.62

0.00

1.24

1.28

1.31

1.58

2.77

2.80

4.07

4.11

4.20

4.24

4.27

4.31

4.95

4.97

4.98

5.01

5.07

6.96

6.97

7.00

7.01

7.26

7.30

7.34

7.35

7.36

7.39

7.42

(CDCl3, 25 °C)18

OBn

CO2Et

ONsHO

OBn

CO2Et

N3HO

19CDCl3, 25 °C


8

Wed3av2#063.001.001.1r.esp


14.0

4

62.1

3

66.7

8

69.9

873

.66

76.3

777

.00

77.6

4

114.

90

127.

4312

7.93

127.

9912

8.58

131.

28

136.

72

159.

04

168.

95

Wed3av2#063.002.001.1r.esp


14.1

3

62.2

0

66.8

4

70.0

4

73.7

4

114.

97

127.

5112

8.01

128.

65

OBn

CO2Et

N3HO

19CDCl3, 25 °C

OBn

CO2Et

N3HO

19CDCl3, 25 °C


9

Mon4av2#009.001.001.1r.esp

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

3.008.782.750.822.060.880.831.991.904.82

1.15

1.19

1.22

1.43

4.04

4.08

4.11

4.15

4.18

4.61

4.63

4.65

4.67

5.04

5.12

5.30

5.34

6.90

6.94

6.95

7.17

7.21

7.33

7.35

7.37

7.37

7.39

7.40

7.41

OBn

CO2Et

NHBocHO

20(CDCl3, 25 °C)

OXABOC_13C-2.jdf


13.9

7

28.1

9

59.6

761

.62

69.9

174

.60

76.6

777

.00

77.3

280

.50

114.

52

127.

2912

7.38

127.

9012

8.51

131.

57

136.

84

156.

3315

8.48

169.

85

CO2Et

NHBocHO

OBn

(CDCl3, 25 °C)20


10

OXABOX_DEPT-2.jdf

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)

128.

6712

8.06

127.

5412

7.44

114.

67

74.7

6

70.0

7

61.7

859

.82

28.3

4

14.1

3

CO2Et

NHBocHO

OBn(CDCl3, 25 °C)

20

Thu3av2#009.001.001.1r.esp

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)

3.004.1610.983.159.402.060.873.030.812.197.58

-0.1

9

0.00

0.01

0.84

1.01

1.05

1.08

1.34

3.93

3.96

4.00

4.03

4.38

4.40

4.43

4.45

4.94

5.20

5.24

6.83

6.87

7.18

7.21

7.22

7.24

7.25

7.28

7.31

7.34

7.35

OBn

CO2Et

NHBocTBSO

(CDCl3, 25 °C)

22


11

Sat3av2#059.002.001.1r.esp

192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8Chemical Shift (ppm)

-5.5

3-5

.02

13.7

9

17.8

8

25.5

028

.09

60.6

060

.77

69.6

774

.94

76.3

777

.00

77.6

479

.34

114.

03

127.

2312

7.68

128.

3013

2.70

136.

78

154.

61

158.

07

169.

70

OBn

CO2Et

NHBocTBSO

(CDCl3, 25 °C)22

Sat3av2#059.001.001.1r.esp

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8Chemical Shift (ppm)

-5.2

6-4

.75

14.0

6

25.7

728

.36

60.8

7

61.04

69.93

75.2

1

114.

29

127.

5112

8.57

OBn

CO2Et

NHBocTBSO

(CDCl3, 25 °C)22


12

Thu3av2#008.001.001.1r.esp

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)

3.023.009.132.799.021.980.770.890.762.032.020.95

-0.1

9

0.00

0.84

1.08

1.12

1.15

1.37

3.99

4.03

4.06

4.10

4.41

4.43

4.45

4.47

4.92

4.94

5.25

5.29

6.71

6.75

7.09

7.14

7.25

7.49

OH

CO2Et

NHBocTBSO

(CDCl3, 25 °C)24

Sat3av2#057.002.001.1r.esp


-5.5

0-4

.94

13.8

3

17.9

3

25.5

328

.17

60.7

361

.21

75.0

776

.36

77.0

077

.64

80.1

0

114.

91

127.

38

131.

34

155.

1515

5.99

170.

37

OH

CO2Et

NHBocTBSO

(CDCl3, 25 °C)24


13

Sat3av2#057.001.001.1r.esp

160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8Chemical Shift (ppm)

-5.3

7-4

.81

13.9

7

25.6

728

.07

28.3

1

60.8

561

.35

75.1

9

115.

04

127.

51

OH

CO2Et

NHBocTBSO

(CDCl3, 25 °C)24

Fri3av2#014.001.001.1r.esp

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)

3.032.979.123.069.012.001.942.090.860.880.832.042.11

-0.1

9

0.00

0.84

1.07

1.10

1.14

1.36

2.74

2.77

2.80

3.97

4.01

4.04

4.08

4.10

4.13

4.16

4.41

4.94

4.96

5.18

5.22

6.78

6.83

7.21

7.23

7.25

O

CO2Et

NHBocTBSO

CN

(CDCl3, 25 °C)26


14

Sat3av2#079.002.001.1r.esp

184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8Chemical Shift (ppm)

-5.4

4-4

.96

13.9

317

.97

18.4

9

25.5

528

.18

60.7

260

.98

62.4

9

74.9

876

.37

77.0

077

.64

79.6

1

113.

95

117.

13

127.

49

133.

86

154.

7115

7.04

169.

65

O

CO2Et

NHBocTBSO

CN(CDCl3, 25 °C)

26

Sat3av2#079.001.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8Chemical Shift (ppm)

-5.4

1-4

.93

13.9

6

18.5

3

25.5

8

28.2

1

60.7

561

.01

62.5

1

75.0

0

113.

97

127.

52

O

CO2Et

NHBocTBSO

CN(CDCl3, 25 °C)

26


15

Sat3av2#011.001.001.1r.esp

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

3.003.139.719.232.272.141.082.140.920.822.142.42

-0.1

8

0.00

0.84

1.38

2.73

2.76

2.79

3.34

3.40

3.45

3.48

3.72

3.74

3.78

3.79

4.09

4.12

4.15

5.06

5.37

5.41

6.79

6.83

7.23

7.27

O

CH2OH

NHBocTBSO

CN(CDCl3, 25 °C)

26a

Tue3av2#073.002.001.1r.esp


-5.4

8-5

.05

17.9

618

.52

25.7

028

.31

56.5

6

60.9

762

.52

76.3

676

.85

77.0

077

.63

79.4

1

114.

3111

7.10

127.

13

134.

34

155.

5515

6.93

O

CH2OH

NHBocTBSO

CN

26a

(CDCl3, 25 °C)


16

Tue3av2#073.001.001.1r.esp

160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8Chemical Shift (ppm)

-5.5

0-5

.07

18.5

1

25.6

8

28.2

9

56.5

2

60.9

462

.49

76.8

3

114.

28

127.

10

O

CH2OH

NHBocTBSO

CN

26a(CDCl3, 25 °C)

Thu1av2#001.001.001.1r.esp

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

2.813.019.002.270.851.572.400.750.662.342.530.83

-0.1

5

0.05

0.90

2.80

2.83

2.86

3.40

3.42

3.46

3.48

3.86

3.87

3.93

3.96

3.98

4.15

4.18

4.21

5.09

5.11

6.49

6.53

6.86

6.91

7.25

7.29

7.33

8.25

CH2OH

NHCHOTBSO

O CN(CDCl3, 25 °C)

27a


17

Sun3av2#022 c13 tbs bursatelline.002.001.1r.esp


-5.2

8-4

.88

17.9

818

.62

25.7

7

54.5

7

60.7

662

.60

76.3

776

.64

77.0

077

.63

114.

5211

7.09

127.

3112

8.02

133.

99

157.

24

161.

00

CH2OH

NHCHOTBSO

O CNCDCl3, 25 °C

27a

Sun3av2#022 c13 tbs bursatelline.001.001.1r.esp


-5.2

2-4

.82

18.6

9

25.8

3

54.5

9

60.8

262

.64

76.7

3

114.

57

127.

36

161.

07

CH2OH

NHCHOTBSO

O CNCDCl3, 25 °C

27a


18

Fri4av400#004.001.001.1r.esp

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)

0.962.000.881.401.241.021.981.000.971.931.800.91

2.57

2.83

2.85

2.87

3.06

3.65

3.68

3.88

3.88

3.91

3.91

4.13

4.14

4.15

4.16

4.20

4.22

4.23

5.06

5.06

6.42

6.43

6.93

6.95

7.27

7.36

7.38

8.27

O

CH2OH

NHCHOHO

CN(CDCl3, 25 °C)

epi-bursatellin (11)

Fri4av400#004.003.001.1r.esp


18.6

6

29.7

1

54.2

3

61.4

062

.74

75.4

376

.69

77.0

177

.22

77.3

3

114.

8511

7.07

127.

21

133.

92

157.

48

161.

28

O

CH2OH

NHCHOHO

CN(CDCl3, 25 °C)



19

Fri4av400#004.002.001.1r.esp


18.6

6

54.2

4

61.4

062

.74

75.4

377

.21

90.3

0

114.

85

127.

21

161.

28

O

CH2OH

NHCHOHO

CN


(CDCl3, 25 °C)

Mon4av2#010.001.001.1r.esp

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)

3.002.959.151.162.000.881.032.042.010.972.014.950.901.000.990.91

-0.1

50.

000.

07

0.92

1.75

2.79

2.82

2.85

3.03

3.06

3.60

3.64

3.68

3.71

3.94

3.95

4.00

4.03

4.05

4.13

4.16

4.19

5.04

5.06

6.84

6.89

7.26

7.29

7.30

7.32

7.34

7.35

7.36

7.41

7.42

8.10

8.15

8.41

8.43

8.44

8.45

8.87

8.89

9.27

NH

O

HN

O

OCN

OTBS

OH(CDCl3, 25 °C)

27b


20

Mon4av2#057.002.001.1r.esp


-5.2

9-4

.88

17.9

918

.66

25.7

5

56.2

3

61.0

562

.49

75.8

076

.37

77.0

077

.63

111.

6811

3.20

114.

3811

7.40

122.

4012

3.32

124.

1612

6.53

127.

52

134.

1813

5.72

138.

05

157.

17

162.

47

180.

36

NH

O

HN

O

OCN

OTBS

OH

(CDCl3, 25 °C)27b

Mon4av2#057.001.001.1r.esp

168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8Chemical Shift (ppm)

-5.2

3-4

.82

18.7

2

25.8

1

56.2

8

61.1

162

.54

75.8

7

111.

74

114.

44

122.

4612

3.39

124.

2212

7.58

138.

13

NH

O

HN

O

OCN

OTBS

OH

(CDCl3, 25 °C)27b


21

Thu4av2#008.001.001.1r.esp

10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

1.812.000.891.970.932.960.982.014.110.970.860.990.980.58

0.00

2.78

2.81

2.84

3.20

3.23

3.26

3.60

3.66

3.68

3.73

3.76

3.79

3.91

3.93

4.09

4.12

4.15

4.17

4.80

4.82

4.83

4.85

6.85

6.88

6.89

7.25

7.27

7.28

7.29

7.30

7.32

7.32

7.36

7.51

7.54

7.69

8.25

8.26

8.29

8.77

8.78

10.1

9

NH

O

HN

O

OCN

OH

OH

Synthetic epi-Preoxazinin-7 (10)(200 MHz, CD3CN, 25 °C)

ALOK.ESP


0.85

1.26

1.67

2.09

2.50

2.91

19.4

6

57.4

9

62.2

064

.25

74.2

5

113.

6211

3.72

115.

4711

8.69

119.

6012

2.98

124.

2212

5.12

127.

8312

9.26

136.

2913

7.49

140.

11

158.

73

163.

72

182.

38

NH

O

HN

O

OCN

OH

OH



22

ALOKDEPT.ESP

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)

19.4

6

57.4

8

62.1

964

.23

74.2

2

113.

6211

5.45

122.

9812

4.23

125.

1212

9.25

140.

13

NH

O

HN

O

OCN

OH

OH


22 Dec 2010

Acquisition Time (sec) 7.9167 Comment Alok/10997 Date 28/04/2010 11:04:28

Frequency (MHz) 200.13 Nucleus 1H Original Points Count 32768 Points Count 32768 Sweep Width (Hz) 4139.07


1 0 . 0 9 . 5 9 . 0 8 . 5 8 . 0 7 . 5 7 . 0 6 . 5 6 . 0 5 . 5 5 . 0 4 . 5 4 . 0 3 . 5 3 . 0 2 . 5 2 . 0 1 . 5 1 . 0 0 . 5 0 . 0

1 1 . 9 77 . 0 2 2 . 9 92 . 0 0 2 . 0 0 0 . 9 30 . 9 10 . 8 6

0.00

1.19

1.22

1.35

2.91

4.12

4.16

4.19

4.23

4.47

5.04

5.12

5.33

6.92

6.96

6.97

7.24

7.26

7.38

7.40

7.43


23

22 Dec 2010


Frequency (MHz) 50.32 Nucleus 13C Original Points Count 32768 Points Count 32768 Sweep Width (Hz) 11990.41


2 0 0 1 9 0 1 8 0 1 7 0 1 6 0 1 5 0 1 4 0 1 3 0 1 2 0 1 1 0 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 1 0 0

14.1

2

28.2

4

59.6

661

.67

70.0

1

73.7

376

.47

77.1

177

.74

80.0

9

114.

71

127.

4112

7.46

128.

62

132.

37136.

94

158.

59

171.

02

22 Dec 2010




1 8 0 1 7 0 1 6 0 1 5 0 1 4 0 1 3 0 1 2 0 1 1 0 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 1 0 0

14.1

3

28.2

4

61.6870.01

73.7

2

114.

70

127.

4712

8.63


24

22 Dec 2010




1 0 . 0 9 . 5 9 . 0 8 . 5 8 . 0 7 . 5 7 . 0 6 . 5 6 . 0 5 . 5 5 . 0 4 . 5 4 . 0 3 . 5 3 . 0 2 . 5 2 . 0 1 . 5 1 . 0 0 . 5 0 . 0 - 0 . 5 - 1 . 0

1 2 . 0 58 . 9 57 . 0 2 3 . 6 0 3 . 1 13 . 0 12 . 0 0

-0.1

50.

00

0.89

1.18

1.27

1.31

1.35

4.21

4.35

4.41

5.05

5.24

6.91

6.96

7.25

7.29

7.36

7.37

7.40

7.40

7.42

7.44

22 Dec 2010

Acquisition Time (sec) 2.7329 Comment Alok Ranjan Date 18/04/2010 05:15:18



2 0 0 1 9 0 1 8 0 1 7 0 1 6 0 1 5 0 1 4 0 1 3 0 1 2 0 1 1 0 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 1 0 0 - 1 0 - 2 0

-5.2

6-4

.75

14.0

6

18.1

5

25.7

728

.35

61.0

4

69.9

4

75.2

1

79.6

1

114.

30

127.

5012

8.57

132.

97

137.

05

154.

8815

8.34

169.

97

CO2Et

NHBocTBSO

OBn

23

(CDCl3, 25 °C)

CO2Et

NHBocTBSO

OBn

23

(CDCl3, 25 °C)


25

22 Dec 2010




1 8 0 1 7 0 1 6 0 1 5 0 1 4 0 1 3 0 1 2 0 1 1 0 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 1 0 0 - 1 0

-5.2

6-4

.75

14.0

6

25.7

728

.35

60.8

761

.04

69.9

3

75.2

1

114.

29

127.

5112

7.96

128.

57

28 May 2011Alok/10997 ( 303K)

Z:\AV400\JAN_11~1\SUN4AV~1\2\pdata\1\1r

Acquisition Time (sec) 3.9846 Comment Alok/10997 ( 303K) Date 16/01/2011 16:21:56



9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5

12.58 9.313.07 3.032.011.97 1.050.84

-0.1

5

0.01

0.89

1.27

1.36

4.14

4.17

4.19

4.21

4.24

5.22

5.49

5.51

6.77

6.79

6.97

7.21

7.23

CO2Et

NHBocTBSO

OBn

23

(CDCl3, 25 °C)

CO2Et

NHBocTBSO

OH

25

CDCl3, 25 °C


26

22 Dec 2010

Acquisition Time (sec) 1.3631 Date 22/12/2010 20:26:28 Frequency (MHz) 100.61 Nucleus 13C

Original Points Count 32768 Points Count 32768 Sweep Width (Hz) 24038.46 Temperature (grad C) 0.000

2 0 0 1 9 0 1 8 0 1 7 0 1 6 0 1 5 0 1 4 0 1 3 0 1 2 0 1 1 0 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 1 0 0 - 1 0

-5.5

5-4

.59

14.1

1

18.0

7

25.6

828

.29

60.8

361

.63

74.5

576

.74

77.0

677

.38

80.2

3

115.

04

127.

42

131.

84

155.

8815

6.07

170.

87

22 Dec 2010



2 0 0 1 9 0 1 8 0 1 7 0 1 6 0 1 5 0 1 4 0 1 3 0 1 2 0 1 1 0 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 1 0 0

14.1

1

25.6

828

.29

60.8

361

.63

62.1

6

74.5

5

115.

04

127.

42

CO2Et

NHBocTBSO

OH

25

CDCl3, 25 °C

CO2Et

NHBocTBSO

OH

25

CDCl3, 25 °C


27

2 May 2011Alok/10997




9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5 -1.0

12.09 8.985.05 2.992.06 2.00 1.981.92

-0.1

50.

00

0.89

1.19

1.28

1.32

1.35

2.79

2.82

2.85

4.15

4.18

4.21

4.25

4.34

4.35

4.39

4.40

5.20

5.25

5.30

6.85

6.89

7.27

7.31

9 May 2011Alok/10997




200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10

Chloroform-d

-5.6

9-4

.77

13.9

817

.89

18.4

1

25.5

028

.08

60.4

661

.32

62.4

7

74.2

276

.37

77.0

077

.64

79.4

6

114.

0611

7.09

127.

48

133.

94

155.

2615

7.08

170.

46


28

9 May 2011Alok/10997




180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10

-5.5

2-4

.60

14.1

5

18.5

7

25.6

628

.24

60.6

361

.49

62.6

3

74.3

8

114.

21

127.

64

20 Jan 2011




9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5 -1.0

9.229.043.10 3.002.272.12 2.062.02 1.56

TMS

-0.1

6

0.05

0.88

0.90

1.37

2.79

2.82

2.86

3.62

4.14

4.18

4.21

4.88

4.89

6.83

6.84

6.87

7.22

7.27

CH2OH

NHBocTBSO

O CNCDCl3, 25 °C

28


29

30 May 2011Alok/10997

Z:\AV200\MAY_10~1\data\ADMINI~1\nmr\SA0B7F~1\2\pdata\1\1r




180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10

Chloroform-d

-5.3

2-4

.70

18.0

218

.51

25.7

228

.21

58.4

9

62.5

162

.73

72.9

276

.37

77.0

077

.64

79.4

8

114.

1911

7.16

127.

56

135.

02

156.

0615

6.97

30 May 2011Alok/10997

Z:\AV200\MAY_10~1\data\ADMINI~1\nmr\SA0B7F~1\1\pdata\1\1r




180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10

-5.2

0-4

.59

18.6

3

25.8

428

.33

58.6

0

62.6

262

.86

73.0

3

114.

30

127.

68

CH2OH

NHBocTBSO

O CNCDCl3, 25 °C

28

CH2OH

NHBocTBSO

O CNCDCl3, 25 °C

28


30

20 May 20111H

Acquisition Time (sec) 3.2768 Comment 1H Date 25/05/2010 22:14:54 Frequency (MHz) 500.13



10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0

9.51 3.012.942.51 2.182.03 2.00 1.861.000.970.94

TMS

-0.1

40.

000.

08

0.91

2.82

2.83

2.84

3.67

3.69

4.03

4.04

4.05

4.17

4.19

4.20

4.80

4.81

4.97

6.07

6.08

6.85

6.87

7.24

7.27

8.14

TBS-Protected Bursatellin20 May 201113C

Acquisition Time (sec) 1.1010 Comment 13C Date 26/05/2010 13:13:32 Frequency (MHz) 125.76



200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10

-5.2

2-4

.58

18.1

518

.65

25.8

3

57.1

960

.78

62.6

262

.97

72.2

773

.46

114.

4811

7.17

127.

3912

7.79

134.

68

157.

25

161.

59

164.

99


31

TBS-Protected Bursatellin20 May 2011Alok/10997




200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10

-5.2

0-4

.59

18.6

5

25.7

8

62.1

862

.58

71.9

473

.41

114.

38

127.

3912

7.85

161.

89

(-)-Bursatellin19 May 2011Thu2av400#009Alok




10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0

2.08 2.022.01 1.99 1.901.210.76

methenol

2.78

2.79

2.81

3.19

3.35

3.36

3.39

3.52

3.54

3.56

3.98

3.99

4.05

4.06

4.08

4.78

4.79

6.80

6.82

7.21

7.23

7.89


32





200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

19.0

0

57.1

3

62.5

264

.19

71.9

2

115.

34

119.

17

128.

64

136.

73

158.

87

164.

00





220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20

16.0

4

54.1

7

59.5

661

.22

68.9

5

112.

37

125.

68

161.

04


33

3 Jan 2011




10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5

9.385.50 3.12 3.002.102.10 2.061.02 1.001.00 0.990.97

TMS

-0.1

50.

000.

07

0.92

2.71

2.73

2.74

3.74

3.79

4.02

5.00

6.72

6.74

7.21

7.24

7.26

7.29

7.31

7.34

7.36

7.91

7.93

8.38

8.40

8.70

8.71

8.72

9.58

3 Jan 2011




200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10

Chloroform-d

-5.2

5-4

.61

18.1

018

.55

25.7

8

58.1

1

62.3

662

.73

72.7

376

.69

77.0

077

.32

111.

8511

2.94

114.

2711

7.43

122.

2112

3.27

124.

0612

6.51

127.

44

134.

7413

5.80

138.

50

157.

06

163.

00

180.

25


34

3 Jan 2011

Acquisition Time (sec) 1.3631 Comment DEPT Date 03/01/2011 16:27:42 Frequency (MHz) 100.61



200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

18.6

0

25.8

3

58.1

6

62.4

162

.78

72.7

8

111.

8911

4.31

122.

2612

3.32

124.

1112

7.49

138.

56


35

Preoxazinin18 May 2011Thu2av400#009Alok R/10997

Acquisition Time (sec) 3.9846 Comment Alok R/10997 Date 17/05/2010 21:04:00



11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5

4.13 2.03 2.001.96 1.181.03 1.010.950.93 0.910.77

TMSAcetonitrile-d3

-0.0

1

2.16

2.78

2.80

2.81

3.16

3.18

3.59

3.62

3.64

3.68

3.70

3.84

4.04

4.06

4.11

4.13

4.14

4.98

4.98

6.86

6.88

7.29

7.30

7.32

7.52

7.53

7.54

7.55

7.77

7.80

8.31

8.81

10.1

2


36

23 Dec 2010




2 0 0 1 9 0 1 8 0 1 7 0 1 6 0 1 5 0 1 4 0 1 3 0 1 2 0 1 1 0 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 1 0 0

A c e t o n it r ile - d 3

19.1

9

57.7

8

63.1

264

.00

72.5

0

113.

3311

5.25

118.

3812

2.74

123.

9712

4.86

128.

47

136.

5013

7.21

139.

88

158.

38

163.

59

181.

99

23 Dec 2010




1 9 0 1 8 0 1 7 0 1 6 0 1 5 0 1 4 0 1 3 0 1 2 0 1 1 0 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 1 0

18.1

3

56.7

2

62.0

662

.94

71.4

3

112.

2711

4.19

121.

6812

2.90

123.

7912

7.41

138.

81NH

O

HN

O

OCN

OH

OH

Synthetic Preoxazinin-7 (7)(100 MHz, CD3CN, 25 °C)

NH

O

HN

O

OCN

OH

OH

Synthetic Preoxazinin-7 (7)(100 MHz, CD3CN, 25 °C)


37

TBS-protected oxazinin-528 Apr 2011mon5av400#002VHP




8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5

9.494.00 3.103.032.19 2.112.112.09 1.071.051.03 1.031.001.00

TMS

-0.1

9

0.00

0.10

0.91

2.81

2.83

2.84

3.39

3.40

3.42

3.43

3.60

3.61

3.63

3.66

3.67

4.17

4.18

4.20

4.62

4.64

5.51

6.55

6.88

6.90

7.10

7.12

7.15

7.17

7.18

7.26

7.28

7.30

7.32

7.67

7.69

8.35

TBS-protected oxazinin-528 Apr 2011mon5av400#00213C




170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10

Chloroform-d

18.1

118

.60

25.8

1

58.5

961

.45

62.5

8

73.7

976

.19

76.6

877

.00

77.3

2

111.

31

114.

7211

7.05

119.

4912

0.03

122.

3912

4.60

126.

1012

8.24

133.

67

136.

42

157.

79

169.

37


38

TBS-protected oxazinin-528 Apr 2011mon5av400#002DEPT




170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10

-4.9

7-4

.48

18.6

0

25.8

1

58.5

961

.45

62.5

7

73.7

976

.17

111.

31

114.

71

119.

4912

0.03

122.

3912

4.61

128.

24

TBS-protected oxazinin-628 Apr 2011wed5av500#009alok

Acquisition Time (sec) 3.2768 Comment alok Date 23/03/2011 17:33:42 Frequency (MHz) 500.13



9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5

9.717.08 3.17 3.082.26 2.082.052.041.06 1.041.02 1.001.00

TMS

-0.2

1

0.00

0.09

0.90

2.78

2.79

2.80

3.45

3.47

3.48

3.53

3.54

3.57

3.62

4.11

4.12

4.14

4.60

4.62

5.51

6.62

6.81

6.82

7.05

7.06

7.11

7.13

7.17

7.19

7.26

7.29

7.30

7.70

7.72

8.65


39

TBS-protected oxazinin-628 Apr 2011wed5av500#00913C




180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10

Chloroform-d

-5.0

0-4

.48

18.0

618

.55

25.7

6

58.6

361

.13

62.5

0

73.7

776

.10

76.7

577

.00

77.2

6

110.

9111

1.49

114.

5611

7.14

119.

4011

9.88

122.

2912

4.94

126.

1612

8.21

133.

47

136.

47

157.

73

169.

67

TBS-protected oxazinin-628 Apr 2011wed5av500#009DEPT135

Acquisition Time (sec) 1.1010 Comment DEPT135 Date 23/03/2011 17:55:36



170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10

-5.0

1-4

.48

18.5

4

25.7

6

58.6

261

.13

62.4

9

73.7

776

.09

111.

48

114.

55

119.

3911

9.88

122.

28

128.

21


40

oxazinin-528 Apr 2011wed3av400#012VHP




9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0

2.102.09 2.05 2.032.02 1.151.10 1.041.031.03 1.000.96

2.84

2.85

2.87

3.47

3.49

3.50

3.52

3.57

3.58

3.60

3.79

3.81

3.86

3.87

4.18

4.19

4.21

4.55

4.56

4.57

4.58

5.29

6.77

6.95

6.95

6.97

7.05

7.14

7.15

7.26

7.27

7.32

7.33

7.35

7.40

7.42

7.58

7.60

9.29

NH

OO

HNO

OH

Synthetic oxazinin-5 (5)(400 MHz, CD3CN, 25 °C)

CN


41

oxazinin-516 May 2011wed3av400#01213C




170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10

18.1

5

29.4

2

57.5

4

63.0

363

.07

73.6

473

.94

111.

4911

1.97

114.

6411

8.18

119.

3712

1.83

125.

2712

6.12

128.

10

134.

0713

6.48

157.

99

169.

22

oxazinin-516 May 2011wed3av400#012DEPT




160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10

18.1

5

29.3

6

57.5

3

63.0

2

73.6

473

.94

111.

49

114.

63

119.

3612

1.83

125.

28

128.

10


42

17 May 2011Mon1av400#005Vijendra

Acquisition Time (sec) 4.0894 Comment Vijendra Date 03/05/2011 10:05:10 Frequency (MHz) 400.13

Nucleus 1H Original Points Count 32768 Points Count 32768 Sweep Width (Hz) 8012.82 Temperature (grad C) 0.000

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5

3.06 3.05 2.05 1.201.06 1.021.00 1.00 1.001.00

3.46

3.47

3.49

3.54

3.55

3.57

3.76

3.78

3.79

3.82

3.82

4.47

4.48

4.49

4.50

5.28

5.44

6.79

6.81

7.02

7.04

7.06

7.12

7.13

7.15

7.19

7.21

7.25

7.38

7.40

7.57

7.59

9.30

17 May 2011Mon1av400#005Vijendra




175 170 165 160 155 150 145 140 135 130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55

57.5

9

63.1

9

73.6

274

.10

111.

5011

1.90

115.

21

117.

35

119.

36

121.

83

125.

3012

6.15

128.

01

132.

17

136.

44

156.

89

169.

30


43

17 May 2011Mon1av400#005DEPT




170 160 150 140 130 120 110 100 90 80 70 60 50 40

57.5

9

63.1

9

73.6

174

.10

111.

51

115.

21

119.

37

121.

83

125.

31

128.

02


44

oxazinin-617 May 2011sat5av400#0091H



9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0

2.20 2.17 2.162.06 2.05 1.021.02 1.021.01 1.00

2.83

2.84

2.86

3.56

3.57

3.59

3.60

3.61

3.62

3.63

3.91

3.92

4.16

4.17

4.19

4.70

4.71

4.72

4.73

5.38

6.86

6.91

6.93

7.05

7.07

7.09

7.15

7.16

7.23

7.24

7.27

7.29

7.42

7.44

7.61

7.63

9.37

oxazinin-617 May 2011sat5av400#00913c

Acquisition Time (sec) 1.3631 Comment 13c Date 01/05/2011 09:36:18 Frequency (MHz) 100.61



180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10

19.0

4

30.5

9

58.1

8

62.6

564

.18

74.4

675

.25

112.

4711

2.75

115.

5911

8.41

119.

2112

0.19

120.

5912

2.74

126.

2712

7.29

129.

29

135.

3913

7.34

158.

84

170.

06


45

oxazinin-617 May 2011sat5av400#009Vijendra




170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20

19.0

4

30.2

5

58.3

3

62.6

463

.89

74.3

875

.22

112.

40

115.

4211

5.53

120.

2212

0.33

122.

73

126.

24

129.

13

17 May 2011Thu2av400#0091H side product



10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5

6.11 4.002.09 1.031.01 1.00 1.000.98 0.98

3.54

3.55

3.57

3.58

3.59

3.83

4.65

5.38

6.76

6.79

6.87

7.06

7.07

7.09

7.14

7.17

7.23

7.42

7.44

7.62

7.64

9.38


46

17 May 2011Thu2av400#00913C side product




175 170 165 160 155 150 145 140 135 130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55

58.5

6

62.7

8

74.4

675

.56

112.

5611

2.67

116.

1711

8.40

120.

3712

0.48

122.

88

126.

4212

7.47

129.

18

133.

44

137.

49

157.

84

170.

20

17 May 2011Thu2av400#009DEPT, side product



170 160 150 140 130 120 110 100 90 80 70 60 50 40

57.5

1

61.7

4

73.4

274

.52

111.

52

115.

13

119.

3211

9.44

121.

83

125.

38

128.

15


47

TBSPROTDED2_1H-4.jdf

10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)

3.053.009.463.332.102.061.081.050.991.012.124.100.970.940.830.950.90

-0.1

5

0.02

0.91

1.30

1.31

1.33

2.71

2.73

2.74

4.02

4.04

4.04

4.18

4.20

4.22

4.26

4.29

4.29

4.69

4.69

4.71

4.71

5.39

5.39

6.73

6.75

7.26

7.27

7.29

7.30

7.31

7.34

7.35

8.10

8.12

8.35

8.37

8.54

8.55

9.43

TBSPROTETED2_13C-1.jdf

200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0 -8Chemical Shift (ppm)

-5.5

4-4

.57

14.1

018

.04

18.5

9

25.6

6

59.4

361

.92

62.3

7

74.3

376

.75

77.0

077

.26

111.

7811

2.93

114.

2111

7.53

122.

2012

3.23

124.

0412

6.41

127.

4913

3.72

135.

7813

8.24

157.

25

162.

29

169.

49

179.

92

NH

HN

O

O

OTBS

CO2Et OCN

(CDCl3, 25 °C)34

NH

HN

O

O

OTBS

CO2Et OCN

(CDCl3, 25 °C)34


48

TBSPROTETED2_DEPT135-4.jdf


-5.4

2-4

.46

14.2

2

18.7

2

25.7

8

59.5

562

.04

62.4

9

74.4

6

111.

9011

4.32

122.

3112

3.35

124.

1512

7.61

138.

37

OXAOXADEPNOTE2_1H-4.jdf

10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)

3.212.115.261.021.002.134.150.970.920.970.940.80

1.20

1.21

1.23

2.76

2.77

2.79

4.01

4.08

4.09

4.10

4.11

4.15

4.16

4.18

4.19

4.66

4.67

4.68

4.69

5.27

6.84

6.85

7.26

7.27

7.27

7.28

7.30

7.32

7.49

7.50

7.51

7.95

7.96

8.25

8.26

8.26

8.68

8.68

10.1

4

NH

HN

O

O

OTBS

CO2Et OCN

(CDCl3, 25 °C)34

(CDCl3, 25 °C)35

NH

HN

O

O

OH

CO2Et OCN


49

OXADEPNOTE2_13C-1.jdf


14.8

3

19.4

8

59.9

062

.85

64.3

2

73.6

1

113.

6911

5.61

119.

5612

3.07

124.

3612

5.26

127.

8312

8.81

135.

1113

7.57

140.

20

158.

97

163.

72

170.

96

181.

60

NH

HN

O

O

OH

CO2Et OCN

(CDCl3, 25 °C)35

OXADEPNOTE2_DEPT135-3.jdf


14.8

4

19.4

8

59.8

962

.87

64.3

0

73.5

8

113.

7011

5.58

123.

0612

4.36

125.

2612

8.80

140.

23

NH

HN

O

O

OH

CO2Et OCN

(CDCl3, 25 °C)35


50

OXA_ZININ15_1H-4.jdf


2.000.641.001.000.992.020.990.890.931.940.940.951.930.930.930.940.70

2.8

12

.82

2.8

3

3.0

63

.27

3.2

83

.29

3.4

23

.45

3.7

13

.72

3.7

23

.74

3.7

4

4.1

44

.15

4.1

6

4.6

24

.63

5.5

9

6.6

66

.88

6.8

96

.98

7.0

07

.01

7.1

27

.14

7.1

57

.20

7.2

27

.30

7.4

27

.44

7.5

87

.60

9.3

9

OXAZININE18_13C-4.jdf

200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)

19.0

0

59.8

561

.96

63.8

8

71.0

172

.89

112.

4411

5.43

119.

0912

0.04

120.

3512

2.84

126.

1112

7.48

129.

9613

1.80

137.

43

158.

98

170.

19

O

HN

OH

O

HN OCN


O

HN

OH

O

HN OCN



51

OXAZININ15_DEPT135-4.jdf

176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8Chemical Shift (ppm)

19.0

0

30.2

5

59.8

561

.99

63.9

0

71.0

372

.91

112.

47

115.

43

120.

1212

0.35

122.

85

126.

09

129.

96

OXAZ42_1H-4.jdf

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5Chemical Shift (ppm)

2.011.010.800.872.030.870.870.771.861.553.970.800.71

2.79

2.80

2.81

3.25

3.27

3.28

3.29

3.30

3.40

3.42

3.86

4.13

4.14

4.15

4.71

4.73

5.42

6.69

6.90

6.92

7.06

7.07

7.12

7.14

7.30

7.33

7.35

7.38

7.40

7.66

7.67

9.26

O

HN

OH

O

HN OCN


O

HN

OH

O

HN OCN



52

OXAZININE47_13C-4.jdf


19.2

0

60.7

861

.98

64.1

2

75.6

877

.95

112.

6111

3.41

115.

7011

9.29

120.

4612

0.62

122.

8912

6.39

127.

1612

9.92

132.

07

137.

57

159.

28

170.

79

OXAZININE47_DEPT135-5.jdf


19.2

0

60.7

761

.95

64.0

9

75.6

677

.93

112.

61

115.

67

120.

6012

2.89

126.

40

129.

91

O

HN

OH

O

HN OCN


O

HN

OH

O

HN OCN



53

OXA26_1H-4.jdf


1.351.021.001.000.890.842.000.892.070.930.821.220.57

3.01

3.25

3.39

3.42

3.68

3.68

3.69

3.70

3.71

4.54

4.56

5.55

6.62

6.71

6.73

6.98

7.00

7.06

7.08

7.11

7.12

7.27

7.27

7.40

7.42

7.56

7.58

9.35

OXAXINI29_13C-5.jdf


59.9

062

.11

71.2

372

.91

112.

4211

2.48

116.

05

120.

1212

0.39

122.

8812

6.12

127.

5012

9.95

130.

07

137.

48

158.

01

170.

23

O

HN

OH

O

HN OH


O

HN

OH

O

HN OH



54

OXAXINI29_DEPT135-4.jdf


59.9

062

.08

71.2

072

.89

112.

4711

6.03

118.

3312

0.11

120.

3712

2.86

126.

11

129.

93

Reported CD Spectra of Natural Oxazinin-5 (5):

O

HN

OH

O

HN OH



55

CD Spectra of Synthetic Oxazinin-5 (5):

200 220 240 260 280 300 320-20

-15

-10

-5

0

5

10

15

20

25

30

md

eg

Wavelength(nm)

Reported CD spectra of Natural Preoxazinin-7 (7):


56

CD spectra of Synthetic Preoxazinin -7 (7):

Reported CD spectra of Natural Oxazinin-6 (6):


57

CD Spectra of Synthetic oxazinin-6 (6):

220 240 260 280 300

-4

-2

0

2

4

6

8

10

Elip

ticity

(m

*)

Wavelength(nm)


58

Enantiomeric excess of (2S,3R)-ethyl 3-(4-(benzyloxy)phenyl)-2-(tert-

butoxycarbonylamino)-3-hydroxypropanoate (Recemic):


59

Enantiomeric excess of (2S,3R)-ethyl 3-(4-(benzyloxy)phenyl)-2-(tert-

butoxycarbonylamino)-3-hydroxypropanoate (21) (Chiral):


supporting information - the royal society of chemistry supporting information enantioselective...

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