Post on 02-Oct-2020
transcript
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