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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