Catalytic Reactions with Hydrosilane and Carbon Monoxide [New synthetic methods (30)]

The reagent hydrosilane/carbon monoxide opens up new possibilities for organic synthesis. Four cases will be discussed: 1. The reaction of olefins with hydrosilane (trialkylsilane) and carbon monoxide in the presence of Co, Ru, and Rh complexes leads to enol silyl ethers having one more carbon atom that the olefins. 2. Cyclic ethers underto carbonylative ring opening to ω‐siloxyaldehydes when reacted with hydrosilane and carbon monoxide in the presence of Co 2 (CO) 8 as catalysts 3. Aldehydes are catalytically converted into the next higher α‐siloxyaldehydes or 1,2‐bis(siloxy)alkenes depending on the reaction conditions used. 4. The reaction of alkyl acetates proceeds in various ways depending on the nature of the alkyl group; enol silyl ethers or alkenes are optained.–Mechanisms of these Co 2 (CO) 8 catalyzed reactions using hydrosilane and carbon monoxide are discussed in which HCo(CO) n or R 3 SiCo(CO) n L function as catalytically active agents. With these species there are four types of catalytic cycles.–The synthetic possibilities of these catalytic reactions have still not been fully explored.