Development of New Reactions with Organometallic Reagents Stable in

点击翻译按钮获取中文摘要

The alkylation of aldehydes with organometallic reagents is one of the most important reactions in organic chemistry. Conventional alkylborane reagents do not react with aldehydes. We disclosed that nickel-catalyzed alkylation of aldehydes with trialkylboranes proceeds smoothly in the presence of a catalytic amount of η^2-ally1-1,2,3,4,5-pentamethy1-1,3-cyclopentadiene or an excess of cesium carbonate to afford the corresponding secondary alcohols. Trialkylboranes prepared from borane-dimethyl sulfide and terminal olefins via hydroboration as well as commercially available trialkylboranes could be employed for the reaction. The reaction would proceed via 12-coordinated nickel complexes with aldehydes as key intermediates. Interestingly, water enabled alkylation of aldehydes with trialkylboranes under nickel catalysis without additives.