7378
4. (a) Lee, D.-H.; Lee, S.-W. Tetrahedron Lett. 1997, 38, 7909±7910. (b) Chakraborty, T. K.; Suresh, V. R. Chem.
Lett. 1997, 565±566. (c) Kobayashi, J.; Hatakeyama, A.; Tsuda, M. Tetrahedron 1998, 54, 697±704. (d) Ohi, K.;
Shima, K.; Hamada, K.; Saito, Y.; Yamada, N.; Ohba, S.; Nishiyama, S. Bull. Chem. Soc. Jpn. 1998, 71, 2433±
2440. (e) Ishiyama, H.; Takemura, T.; Tsuda, M.; Kobayashi, J. Tetrahedron 1999, 55, 4583±4594. (f) Eng, H. M.;
Myles, D. C. Tetrahedron Lett. 1999, 40, 2275±2278.
5. For reviews see: (a) Farina, V.; Krishnamurthy, V.; Scott, W. J. in Organic Reactions; Paquette, L. A., Ed. John
Wiley and Sons: New York, 1997; Vol. 50, pp. 1±652. (b) Duncton, M. A. J.; Pattenden, G. J. Chem. Soc., Perkin
Trans. 1 1999, 1235±1246.
6. For the development of copper(I) reagents in the Stille coupling see: (a) Piers, E.; Wong, T. J. Org. Chem. 1993,
58, 3609±3610. (b) Allred, G. D.; Liebeskind, L. S. J. Am. Chem. Soc. 1996, 118, 2748±2749. (c) Paterson, I. Man,
J. Tetrahedron Lett. 1997, 38, 695±698. (d) Han, X., Stoltz, B. M.; Corey, E. J.; J. Am. Chem. Soc. 1999, 121,
7600±7605.
7. Cid, M. B.; Pattenden, G. Synlett 1998, 540±542.
1
1
8. Selected H NMR data (amphidinolide numbering). Alcohol 3 H NMR (360 MHz, CDCl3): ꢀ=6.28 (bs, 1H,
C14 H); 4.18 (m, 2H, C18 H, C21 H); 3.78±3.70 (m, 1H, C25 H); 3.58 (dd, J=5.8, 4.3, 1H, C22 H); 2.80 (dd,
J=18, 4.4, 1H, C19 H); 2.69 (dd, J=18, 7.6, 1H, C19 H); 2.00±1.73 (m, 4H, C17 H2, C24 H and C23 H); 1.89
(s, 3H, CH3); 1.46 (s, 3H, CH3); 1.17 (d, J=6.2, 3H, CH3); 1.13 (m, 1H, C24 H); 0.96 (s, 9H, 3CH3); 0.94 (t,
J=7.8, 9H, 3CH3); 0.92 (s, 9H, 3CH3); 0.88 (s, 9H, 3CH3); 0.85 (d, J=6.6, 3H, CH3); 0.58 (q, J=7.8, 6H, 3CH2);
0.16 (s, 3H, CH3); 0.12 (s, 3H, CH3); 0.10 (s, 3H, CH3); 0.06 (s, 3H, CH3); 0.04 (s, 3H, CH3) and 0.02 (s, 3H, CH3).
Carboxylic acid 4 1H NMR (360 MHz, CDCl3): ꢀ=6.88 (bt, J=6.6, 1H, C3 H); 5.90 (dt, J=15.4, 6.1, 1H,
C6 H); 5.63 (bs, JSn H=152, 1H, C28 H); 5.25 (dd, J=15.4, 8, 1H, C7 H); 5.20 (bs, JSn H=72, 1H, C28 H);
3.04 (dd, J=8, 1.9, 1H, C8 H); 2.84 (td, J=5.9, 1.9, 1H, C9 H); 2.40±2.14 (m, 6H, C4H2, C5H2, C12H2); 1.85 (bs,
3H, C26H3); 1.80±1.70 (m, 1H, C11 H); 1.65 (dt, J=13.8, 5.9 Hz, 1H, C10 H); 1.27 (ddd, J=13.8, 8.4 and 5.9, 1H,
C10 H); 0.93 (d, J=6.6, 3H, C27 H3); 0.15 (s, JSn H, 54 and 52, 9H, 3CH3).
9. (a) Baudin, J. B.; Hareau, G.; Julia, S. A.; Ruel, O. Tetrahedron Lett. 1991, 32, 1175±1178. (b) Bellingham, R.;
Jarowicki, K.; Kocienski, P.; Martin, V. Synthesis 1996, 285±296. (c) Smith, N. D.; Kocienski, P. J.; Street, S. D. A.
Synthesis 1996, 652±666. (d) Charette, A. B.; Leber, M. J. Am. Chem. Soc. 1996, 118, 10327±10328. (e) Blakemore,
P. R.; Cole, W. J.; Kocienski, P. J.; Morley, A. Synlett 1998, 26±28.
10. Gao, Y.; Hanson, R. M.; Klunder, J. M.; Ko, S. Y.; Masamune, H.; Sharpless, K. B. J. Am. Chem. Soc. 1987, 109,
5765±5780.
11. (a) Mitchell, T. N.; Wickenkamp, R.; Amamria, A.; Dicke, R.; Schneider, U. J. Org. Chem. 1987, 52, 4868±4874.
(b) Chenard, B. L.; Van Zyl, C. M. J. Org Chem. 1986, 51, 3561±3566.
12. The phosphonate 19 was obtained by esteri®cation of trimethylsilylethanol with 2-(diethoxyphosphoryl)propionic
acid which, in turn, was obtained by hydrolysis of 2-(diethoxyphosphonyl)propionic acid ethyl ester as described
by Roush, W. R.; Sciotli, R. J. J. Am. Chem. Soc. 1998, 120, 7411.
13. Blanchette, M. A.; Choy, W.; Davis, J. T.; Essenfeld, A. P.; Masamune, S.; Roush, W. R.; Sakai, T. Tetrahedron
Lett. 1984, 32, 2183±2186.
14. When benzothiazole was used as the heterocycle instead of phenyltetrazole, a lower selectivity (E/Z=2:1) was
observed.
15. When a Pd(0) catalyst under Farina conditions was used, decomposition or no reaction was observed when the
model compound 22 was used.
16. Piers, E.; Romero, M. A. J. Am. Chem. Soc. 1996, 118, 1215±1216.