Selective Hydride-Mediated Conjugate Reduction of α,β-Unsaturated Carbonyl Compounds Using [(Ph3P)CuH]6

Journal of the American Chemical Society

Volumn 110, Issue 1, 1988, Pages 291-293

  Mahoney, Wayne S ^a   Brestensky, Donna M ^a   Stryker, Jeffrey M ^a  

^a INDIANA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33845278094     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00209a048     Document Type: Article

References (16)

1. 4/HMPA, catalytic Cul: Tsuda, T.; Fujii, T.; Kawasaki, K.; Saegusa, T. J. Chem. Soc., Chem. Commun. 1980, 1013. (e) MeCu/DIBAH in the presence of HMPA; electrophilic trapping of the enolate is possible after addition of MeLi to the aluminum enolate: Tsuda, T.; Satomi, H.; Hayashi, T.; Saegusa, T. J. Org. Chem. 1987, 52, 439, and references therein.
2. 3SnH: Brimage, D. R. G.; Davidson, R. S.; Lambeth, P. F. J. Chem. Soc. C 1971, 1241.
3. 5H]: Reger, D. L; Habib, M. M.; Fauth, D. J. Tetrahedron Lett. 1979, 115. Reger, D. L.; Habib, M. M.; Fauth, D. J. J. Org. Chem. 1980, 45, 3860, and references therein. In stoichiometric form, see: Halpern, J.; Wong, L. Y. J. Am. Chem. Soc. 1968, 90, 6665, and references therein.
4. Major improvement in the transition-metal-catalyzed hydrosilation of unsaturated carbonyl compounds, leading directly to carbonyl products, has recently been reported: Keinan, E.; Greenspoon, N. J. Am. Chem. Soc. 1986, 108, 7314. Keinan, E.; Perez, D. J. Org. Chem. 1987, 52, 2576.
5. Churchill, M. R.; Bezman, S. A.; Osborn, J. A.; Wormald, J. Inorg. Chem. 1972, 11, 1818. Bezman, S. A.; Churchill, M. R.; Osborn, J. A.; Wormald, J. J. Am. Chem. Soc. 1971, 93, 2063.
6. Goeden, G. V.; Caulton, K. G. J. Am. Chem. Soc. 1981, 103, 7354.
7. Crystal structure: Lemmen, T. H.; Folting, K.; Huffman, J. C.; Caulton, K. G. J. Am. Chem. Soc. 1985, 107, 7774.
8. Pyridine-stabilized CuH, a pyrophoric material which decomposes in solution above-20 °C, and related thermally unstable phosphine complexes have been reported and demonstrated to be mildly hydridic: (a) Wiberg, E.; Henle, W. Z. Naturforsch., B: Anorg. Chem., Org. Chem., Biochem., Bio phys., Biol. 1952, 7B, 250. (b) Dilts, J. A.; Shriver, D. F. J. Am. Chem. Soc. 1968, 90, 5769. Dilts, J. A.; Shriver, D. F. J. Am. Chem. Soc. 1969, 91, 4088. (c) Whitesides, G. M.; San Filippo, J., Jr.; Stredronsky, E. R.; Casey, C. P. J. Am. Chem. Soc. 1969, 91, 6542.
9. Heterolytic hydrogen activation by other Cu(I) salts has been extensively documented: Calvin, M. Trans. Faraday Soc. 1938, 34, 1181. Calvin, M. J. Am. Chem. Soc. 1939, 61, 2230. Weller, S.; Mills, G. A. J. Am. Chem. Soc. 1953, 75, 769. Wright, L. W.; Weller, S. J. Am. Chem. Soc. 1954, 76, 3345. Wright, L.; Weller, S.; Mills, G. A. J. Phys. Chem. 1955, 59, 1060. Calvin, M.; Wilmarth, W. K. J. Am. Chem. Soc. 1956, 78, 1301. Wilmarth, W. K.; Barsh, M. K. J. Am. Chem. Soc. 1956, 78, 1305. Chalk, A. J.; Halpern, J. J. Am. Chem. Soc. 1959, 81, 5846. Chalk, A. J.; Halpern, J. J. Am. Chem. Soc. 1959, 81, 5852 and references therein.
10. The literature of heterolytic hydrogen activation by transition-metal complexes, particularly the elegant mechanistic work of J. Halpern and B. R. James, has been reviewed on several occasions, see: Brothers, P. J. Prog. Inorg. Chem. 1981, 28, 1.
11. James, B. R. Adv. Organomet. Chem. 1979, 17, 319.
12. James, B. R. Homogeneous Hydrogenation; Wiley: New York, 1973; and references therein.
13. A transition-metal hydride system which reduces saturated carbonyl functionality catalytically, and may involve heterolytic activation of molecular hydrogen, has been reported recently. The chemoselectivity and regioselectivity of this process has not been reported: Tooley, P. A.; Ovalles, C.; Kao, S. C.; Darensbourg, D. J.; Darensbourg, M. Y. J. Am. Chem. Soc. 1986, 108, 5465.
14. Geerts, R. L.; Caulton, K. G., unpublished results.
15. Copper(I) alkoxide complexes have been reported to decompose by both β-elimination and free radical processes: Whitesides, G. M.; Sadowski, J. S.; Lilburn, J. J. Am. Chem. Soc. 1974, 96, 2829.
16. Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923.