Final Problem 2013  You have been provided with MS and NMR data for the macrolactone below.   

O

O OH

OH

Me

Me

Me

+ 7 double bonds   

a.) Use this data to complete the structure by placing all the OH, Me and double bonds in the correct place. 

b.) Assign all the 13C and 1H NMR data to the structure. Provide separate structures showing the 13C and 1H NMR data. 

c.) Provide two separate structures showing the COSY and HMBC data with arrows. d.) Determine the correct geometry of the double bonds (cis or trans?). Can they all be 

determined unequivocally or are there any problems? e.) How would you determine the relative and absolute stereochemistry at the chiral 

centres? What problems might you encounter?   Deadline: Fri 7 Dec 5 pm in my pigeonhole 

Atom # δ 13C (ppm) 13C mult δ 1H (ppm) mult (Hz)

1H-1H COSY HMBC

A B C D E F G H I J K L M N O P Q R S T U V W X Y Z

C:\Documents and Settings\...\C34D_64 05/06/2009 12:07:53

C34D_64 #121 RT: 1.10 AV: 1 NL: 1.22E8F: FTMS + p ESI Full ms [100.00-2000.00]

458 460 462 464 466 468 470 472m/z

0

5000000

10000000

15000000

20000000

25000000

30000000

35000000

40000000

45000000

50000000

55000000

60000000

65000000

70000000

75000000

80000000

85000000

90000000

95000000

100000000

105000000

110000000

115000000

120000000

Inte

nsity

463.2815C 28 H 40 O 4 Na = 463.2819

8.5 RDBE-0.9007 ppm

465.2874C 28 H 42 O 4 Na = 465.2975

7.5 RDBE-21.8735 ppm

466.2899

461.2666C 28 H 38 O 4 Na = 461.2662

9.5 RDBE0.8699 ppm 467.6521 472.3190

1.01.52.02.53.03.54.04.55.05.56.06.57.07.5

C34D_64_CDCl3_1HC34D_64_1H

8.22

1.59

1.22

1.35

2.46

1.71

6.38

4.68

1.89

1.07

1.07

2.79

2.56

4.04

1.03

2.34

1.01

1.00

1.29

3.73.83.94.04.14.24.34.44.54.64.74.84.95.05.15.25.35.45.55.65.75.85.96.06.16.26.36.46.56.66.76.86.97.07.17.27.3

C34D_64_CDCl3_1HC34D_64_1H

1.07

1.07

2.79

2.56

4.04

1.03

2.34

1.01

1.00

1.29

1.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.82.93.03.13.23.33.43.5

C34D_64_CDCl3_1HC34D_64_1H

8.22

1.59

1.22

1.35

2.46

1.71

6.38

4.68

1.89

102030405060708090100110120130140150160170

C34D_64_CDCl3_13CC34D_64_1H

12.3

113

.17

17.0

120

.28

25.2

1

37.3

038

.93

40.7

041

.16

43.7

5

65.5

6

71.5

972

.74

76.6

7 cd

cl3

76.9

9 cd

cl3

77.1

977

.31

cdcl

3

117.

21

125.

4712

7.02

128.

9313

0.60

130.

8813

1.40

131.

7013

2.05

132.

8913

5.19

137.

92

145.

28

148.

23

166.

39

116118120122124126128130132134136138140142144146148150152154156158160162164166168

C34D_64_CDCl3_13CC34D_64_1H

117.21

125.47

127.02

128.93

130.60

130.88

131.40

131.70

132.05

132.89

135.19

137.92

145.28

148.23

166.39

1214161820222426283032343638404244464850525456586062646668707274

C34D_64_CDCl3_13CC34D_64_1H 12

.31

13.17

17.01

20.28

25.21

37.30

38.93

40.70

41.16

43.75

65.56

71.59

72.74

1.01.52.02.53.03.54.04.55.05.56.06.57.0

20

30

40

50

60

70

80

90

100

110

120

130

140

150

C34D_64_hsqcC34D_64_hsqc

5.25.35.45.55.65.75.85.96.06.16.26.36.46.56.66.76.86.97.07.17.27.3

115

120

125

130

135

140

145

150

C34D_64_hsqcC34D_64_hsqc

3.43.53.63.73.83.94.04.14.24.34.44.54.64.74.84.95.05.15.25.35.4

48

50

52

54

56

58

60

62

64

66

68

70

72

74

76

78

80

C34D_64_hsqcC34D_64_hsqc

1.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.6

15

20

25

30

35

40

45

C34D_64_hsqcC34D_64_hsqc

1.01.52.02.53.03.54.04.55.05.56.06.57.0

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

C34D_64_cosyC34D_64_cosy

4.54.64.74.84.95.05.15.25.35.45.55.65.75.85.96.06.16.26.36.46.56.66.76.86.97.07.17.27.37.4

4.6

4.8

5.0

5.2

5.4

5.6

5.8

6.0

6.2

6.4

6.6

6.8

7.0

7.2

7.4

C34D_64_cosyC34D_64_cosy

3.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.6

1.3

1.4

1.5

1.6

1.7

1.8

1.9

2.0

2.1

2.2

2.3

2.4

2.5

2.6

2.7

2.8

C34D_64_cosyC34D_64_cosy

0.60.70.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.62.72.8

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

2.2

2.4

2.6

2.8

C34D_64_cosyC34D_64_cosy

0.51.01.52.02.53.03.54.04.55.05.56.06.57.0

10

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160

170

C34D_64_hmbcC34D_64_hmbc

3.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.4

120

125

130

135

140

145

150

155

160

165

170

C34D_64_hmbcC34D_64_hmbc

0.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.6

115

120

125

130

135

140

145

150

C34D_64_hmbcC34D_64_hmbc

3.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.2

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

C34D_64_hmbcC34D_64_hmbc

0.70.80.91.01.11.21.31.41.51.61.71.81.92.02.12.22.32.42.52.6

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

C34D_64_hmbcC34D_64_hmbc