Direct catalytic enantioselective reduction of achiral α,β-ynones. Strong remote steric effects across the C-C triple bond

Journal of the American Chemical Society

Volumn 118, Issue 44, 1996, Pages 10938-10939

  Helal, Christopher J ^a   Magriotis, Plato A ^a   Corey, E J ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE DERIVATIVE;

ARTICLE; CATALYSIS; CHIRALITY; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0029836898     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja962849e     Document Type: Article

References (31)

1. (a) Nicolaou, K. C.; Webber, S. E. J. Am. Chem. Soc. 1984, 106, 5734.
2. (b) Chemin, D.; Linstramelle, G. Tetrahedron 1992, 48, 1943.
3. (c) Corey, E. J.; Niimura, K.; Konishi, Y.; Hashimoto, S.; Hamada, Y. Tetrahedron Lett. 1986, 27, 2199.
4. Roush, W. R.; Sciotti, R. J. J. Am. Chem, Soc. 1994, 116, 6457.
5. Vourloumis, D.; Kim, K. D.; Petersen, J. L.; Magriotis, P. A. J. Org. Chem, 1996, 61, 4848.
6. (a) Mukaiyama, T.; Suzuki, K.; Soai, K.; Sato, T. Chem. Lett. 1979, 447.
7. (b) Mukaiyama, T.; Suzuki, K. Chem. Lett. 1980, 255.
8. (c) Niwa, S.; Soai, K. J. Chem. Soc., Perkin Trans. 1 1990, 937.
9. (d) Tombo, G. M. R.; Didier, E.; Loubinoux, B. Synlett 1990, 547.
10. (e) Corey, E. J.; Cimprich, K. A. J. Am. Chem. Soc. 1994, 116, 3151
11. (a) Midland, M. M.; Kazubski, A. J. Am. Chem. Soc. 1982,47, 2816.
12. (b) Noyori, R.; Tomino, I.; Yamada, M.; Nishizawa, M. J. Am. Chem. Soc. 1984, 106, 6717.
13. (c) Marshall, J. A.; Robinson, E. D.; Zapata, A. J. Org. Chem. 1989, 54, 5854.
14. (d) Brown, H. C.; Ramachandran, P. V.; Weissman, S. A.; Swaminathan, S. J. Org. Chem. 1990, 55, 6328.
15. Corey, E. J.; Helal, C. J. Tetrahedron Lett. 1995, 36, 9153.
16. 2). The absolute configurations of the other (triisopropylsilyl)acetylenic alcohols (Table 1) were assigned by analogy.
17. +) 300.2723, found 300.2736. The enantioselectivity of the reduction was determined by conversion of the alcohol to the p-nitrobenzoate and HPLC analysis (Chiralcel OD, 0.05% i-PrOH in hexanes, 0.5 mL/min, λ = 254 nm) which showed the product to be of 97% ee (tR = 30.4 min, major; 26.0 min, minor).
18. 0C gave the enantiomer of 2a in 40% ee and 88% yield.
19. S: Parker, K. A.; Ledeboer, M. W. J. Org. Chem. 1996, 61, 3214.
20. (a) Prepared from (trimethylsilyl)acetylene (n-BuLi, THF, -78 °C) and triisopropylsilyl chloride (-78 to 23 °C) in 96% yield after distillation (bp 56-57 °C (0.25 mmHg)). For details see the Supporting Information.
21. (b) For another selective reaction of (triisopropylsilyl)(trimethylsilyl)-acetylene, see: Stang, P. J.; Zhdankin, V. V.; Arif, A. M. J. Am. Chem. Soc. 1991, 113, 8997.
22. The (trimethylsilyl)acetylenic ketones were prepared according to established procedures: (a) Birkofer, L.; Ritter, A.; Uhlenbrauck, H. Chem. Ber. 1963, 96, 3280. (b) Walton, D. R. M.; Waugh, F. J. Organomet, Chem, 1972, 37, 45. (c) Newman, H. J. Org. Chem. 1973, 38, 2254. (d) Earl, R. A.; Vollhardt, K. P. C. J. Org. Chem. 1984, 49, 4786. (e) Reference 3.
23. The (trimethylsilyl)acetylenic ketones were prepared according to established procedures: (a) Birkofer, L.; Ritter, A.; Uhlenbrauck, H. Chem. Ber. 1963, 96, 3280. (b) Walton, D. R. M.; Waugh, F. J. Organomet, Chem, 1972, 37, 45. (c) Newman, H. J. Org. Chem. 1973, 38, 2254. (d) Earl, R. A.; Vollhardt, K. P. C. J. Org. Chem. 1984, 49, 4786. (e) Reference 3.
24. The (trimethylsilyl)acetylenic ketones were prepared according to established procedures: (a) Birkofer, L.; Ritter, A.; Uhlenbrauck, H. Chem. Ber. 1963, 96, 3280. (b) Walton, D. R. M.; Waugh, F. J. Organomet, Chem, 1972, 37, 45. (c) Newman, H. J. Org. Chem. 1973, 38, 2254. (d) Earl, R. A.; Vollhardt, K. P. C. J. Org. Chem. 1984, 49, 4786. (e) Reference 3.
25. The (trimethylsilyl)acetylenic ketones were prepared according to established procedures: (a) Birkofer, L.; Ritter, A.; Uhlenbrauck, H. Chem. Ber. 1963, 96, 3280. (b) Walton, D. R. M.; Waugh, F. J. Organomet, Chem, 1972, 37, 45. (c) Newman, H. J. Org. Chem. 1973, 38, 2254. (d) Earl, R. A.; Vollhardt, K. P. C. J. Org. Chem. 1984, 49, 4786. (e) Reference 3.
26. The (trimethylsilyl)acetylenic ketones were prepared according to established procedures: (a) Birkofer, L.; Ritter, A.; Uhlenbrauck, H. Chem. Ber. 1963, 96, 3280. (b) Walton, D. R. M.; Waugh, F. J. Organomet, Chem, 1972, 37, 45. (c) Newman, H. J. Org. Chem. 1973, 38, 2254. (d) Earl, R. A.; Vollhardt, K. P. C. J. Org. Chem. 1984, 49, 4786. (e) Reference 3.
27. 6 complex of 3-nonyn-2-one also increased with the size of the alkyl group on the boron atom: 87% ee, 3b; 90% ee, B-i-Bu catalyst; 95% ee, 3a. See ref 6.
28. In contrast to the other substrates studied, the reduction of ketone 1c did show a considerable dependence upon the solvent used (product 2c of 53% ee with catalyst 3a in toluene). For other examples of significant solvent effects, see ref 6.
29. (a) Rücker, Ch. Chem, Rev. 1995, 95, 1009.
30. (b) Corey, E. J.; Rücker, Ch. Tetrahedron Lett. 1982, 23, 719.
31. (c) Corey, E. J.; Cho, H.; Rücker, Ch.; Hua, D. H. Tetrahedron Lett. 1981, 22, 3455.