Post on 22-Jun-2020
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)
pwipf+@pitt.edu
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.
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
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
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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