Design of Carbon-Carbon Bond Forming Reactions Starting from the Oxidative Addition of a Hydrosilane to a Rh (I) Complex

摘要

This review describes our recent results on rhodium-catalyzed carbon-carbon bond forming reactions. We have developed two types of multi-component coupling starting from the oxidative addition of a hydrosilane to a low-valent rhodium complex. One type is followed by the insertion of #alpha#,#beta#-unsaturated carbonyl compounds into the resultant Rh-H bond to give a rhodium enolate intermediate which shows sufficient nucleophilicity towards aldehydes, aldimines, isocyanates, and allylic alcohol derivatives to form coupling products. The other type includes the insertion step of alkynes into the Rh-Si bond. This sequence is relayed to silylformylation of an acetylenic bond, selective formation of 2-silylmethylalkenals, silylative lactonization of alkynylalcohols, silylative lactamization of alkynylamines, silylative bicyclocarbonylation of 1,6-diynes, and transannular silylformylation of 1,6-enynes under CO pressure (20 atm).