total synthesis of a stereoisomer of bistramide c and · c nat. bistramide c, 1h [!], mult, (jhh in...
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![Page 1: Total Synthesis of a Stereoisomer of Bistramide C and · C Nat. bistramide C, 1H [!], mult, (JHH in Hz) a Synthetic 1, 1H [!], mult, (JHH in Hz) b Semisynthetic bistramide C, 1H [!],](https://reader036.vdocuments.mx/reader036/viewer/2022081405/5f0afd3e7e708231d42e50c0/html5/thumbnails/1.jpg)
S1Copyright Wiley-VCH Verlag GmbH, 69451, Weinheim, 2002
Chem. Eur. J. 2002
Supporting Information
for
Total Synthesis of a Stereoisomer of Bistramide C and
Assignment of Configuration of the Natural Product
Peter Wipf,* Yoshikazu Uto, and Seiji Yoshimura
Department of Chemistry, University of Pittsburgh
Pittsburgh, Pennsylvania 15260 (USA)
Copies of 1H and 13C NMR as well as HMBC, HMQC, COSY, ROESY, NOESY and DEPT spectrafor 1, and a table comparing NMR data for 1, semisynthetic and natural bistramide C.
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S2Table. Comparison of 1, natural & semisynthetic bistramide C. a400 MHz; b500 MHz; c100 MHz; d151 MHz.
C Nat. bistramide C,1H [!], mult,(JHH in Hz)a
Synthetic 1,1H [!], mult,(JHH in Hz)b
Semisynthetic bistramide C,1H [!], mult,(JHH in Hz)b
Natural bistramide C,13C"!]c
Synthetic 1,13C"!]d
1 1.90, dd,
(6.8, 1.5)
1.92, dd,
(6.8, 1.4)
1.92, dd,
(6.8, 1.5)
18.4 18.6
2 6.88, dq,
(15.9, 6.8)
6.91, dq,
(15.7, 6.9)
6.91, dq,
(15.7, 6.9)
144.2 144.8
3 6.12, dq,
(15.9, 1.7)
6.13, dq,
(15.8, 1.5)
6.13, dq,
(15.9, 1.6)
132.2 132.3
4 --- --- --- 198.4 199.2
5 2.92, dd,
(16.9, 8.8)
2.58, dd,
(16.9, 3.1)
2.91, dd,
(17.0, 9.0)
2.53, dd,
(17.0, 2.8)
2.91, dd,
(17.0, 8.8)
2.53, dd,
(16.9, 2.8)
45.4 45.4
6 4.17, m 4.20, t,
(9.6)
4.20, m 64.9 64.9
7 1.68, m
1.37, m
N/A
N/A
N/A
N/A
30.8 31.0
8 1.62, m
1.33, m
N/A
N/A
N/A
N/A
26.6 26.7
9 1.90 N/A N/A 33.0 33.5
10 0.82, d,
(7.1)
0.86, d,
(7.0)
0.86, d,
(6.9)
17.1 17.4
11 4.06, dd,
(11.8, 4.8)
4.07, dd,
(11.2, 4.9)
4.06, dd,
(11, 5)
74.8 75.0
12 2.73, dd,
(15.4, 11.7)
2.15, m
2.76, dd,
(15.2, 11.7)
2.14, bd,
(15.2)
2.76, dd,
(15.2, 11.7)
2.14, dd,
(15.2, 1.8)
32.5 32.5
13 --- --- --- 173.4 173.7
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S3Table. Continued.
C Nat. bistramide C,1H [!], mult,(JHH in Hz)a
Synthetic 1,1H [!], mult,(JHH in Hz)b
Semisynthetic bistramide C,1H [!], mult,(JHH in Hz)b
Natural bistramide C,13C"!]c
Synthetic 1,13C"!]d
14 3.48, m
3.22, m
3.50, m
3.24, dt,
(13.8, 5.8)
3.52, m
3.23, dt,
(13.8, 6.0)
44.7 44.9
15 3.69, m 3.73, m 3.72, m 73.8 74.0
16 2.38, m 2.39, m 2.38, m 43.4 43.5
17 1.22, d,
(7.1)
1.27, d,
(7.6)
1.27, d,
(7.3)
15.6 15.7
18 --- --- --- 175.1 175.4
19 3.30, m 3.30, m 3.30, m 39.6 39.9
20 1.83, m
1.55, m
N/A
N/A
N/A
N/A
29.9 29.9
21 1.74, m
1.36, m
N/A
N/A
N/A
N/A
30.6 30.7
22 3.15, dt,
(2.2, 9.4)
3.14, dt,
(2.0, 9.7)
3.14, dt,
(1.8, 10.1)
74.3 74.5
23 1.26, m N/A N/A 34.9 35.1
24 0.77, d,
(6.3)
0.82, d,
(6.5)
0.82, d,
(6.5)
18.1 18.2
25 1.58, m
1.44, m
N/A
N/A
N/A
N/A
28.0 28.1
26 1.58, m
1.42, m
N/A
N/A
N/A
N/A
36.2 36.3
27 --- --- --- 95.2 95.7
28 1.52, m
1.38, m
N/A
N/A
N/A
N/A
35.5 35.6
29 1.83, m
1.56, m
N/A
N/A
N/A
N/A
19.2 19.3
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S4Table. Continued.
C Nat. bistramideC, 1H [!], mult,
(JHH in Hz)a
Synthetic 1,1H [!], mult,(JHH in Hz)b
Semisynthetic bistramide C,1H [!], mult,(JHH in Hz)b
Natural bistramide C,13C"!]c
Synthetic 1,13C"!]d
30 1.40, m
1.14, m
N/A
N/A
N/A
N/A
31.4 31.5
31 3.44, m 3.43, m 3.46, m 68.9 69.6
32 1.34, m
1.34, m
N/A
N/A
N/A
N/A
34.8 34.6
33 1.49, m
1.55, m
N/A
N/A
N/A
N/A
33.4 33.5
34 2.58, m 2.60, m 2.56, m 31.8 34.2
35 1.01, d,
(7.1)
1.05, d,
(6.7)
1.05, d
(6.7)
20.1 20.4
36 6.37, dq,
(9.8, 1.2)
6.40, bd,
(9.8)
6.41, bd,
(9.8)
149.3 149.6
37 --- --- --- 136.3 136.5
38 1.73, fd,
(1.2)
1.78, bd 1.77, bd 11.5 11.6
39 --- --- --- 200.2 200.6
40 2.28, s 2.32, s 2.32, s 25.5 25.8
NH
13/14
7.31, br t,
(5.9)
7.32, br t,
(5.5)
7.34, br t,
(6.1)
--- ---
NH
18/19
6.97, br t,
(5.7)
6.96, br t,
(5.5)
6.97, br t,
(5.0)
--- ---
OH
15
4.59, br s 4.61, br s 3.65, br s --- ---
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S18
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S24
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S25
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S26
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S27
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S28
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