Highly Chemoselective Catalytic Hydrogenation of Unsaturated Ketones and Aldehydes to Unsaturated Alcohols Using Phosphine-Stabilized Copper(I) Hydride Complexes

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• 作者：Chen ; Jian-Xin ; Daeuble ; John F. ; Brestensky ; Donna M. ; Stryker ; Jeffrey M.
• 关键词：copper and compounds ; hydrogenation ; catalysis ; carbonyl compounds
• 刊名：Tetrahedron
• 出版年：2000
• 出版时间：April 7, 2000
• 年：2000
• 卷：56
• 期：15
• 页码：2153-2166
• 全文大小：310 K

文摘

A base metal hydrogenation catalyst composed of the phenyldimethylphosphine-stabilized copper(I) hydride complex provides for the highly chemoselective hydrogenation of unsaturated ketones and aldehydes to unsaturated alcohols, including the regioselective 1,2-reduction of α,β-unsaturated ketones and aldehydes to allylic alcohols. The active catalyst can be derived in situ by phosphine exchange using commercial [(Ph₃P)CuH]₆ or from the reaction of copper(I) chloride, sodium tert-butoxide, and dimethylphenylphosphine under hydrogen. The catalyst derived from 1,1,1-tris(diphenylphosphinomethyl)ethane is mechanistically interesting but less synthetically useful.