Catalytic Reduction of Cyclic Ethers with Hydrosilanes

AbstractCatalytic reductive transformations of ethers as a synthetic building block are an important class of chemical reactions because a range of essential chemical feedstocks and fuels in contemporary life can be prepared through the key step of ethereal C−O bond cleavage of cellulosic biomass. Although conventional stoichiometric and catalytic methods for sp2‐ and sp3‐C−O bond cleavage of linear ethers and alcohols with hydrosilanes are well established, silylative ring opening of cyclic ethers has been less highlighted in this context. This review outlines catalytic systems for the silylative reduction of a range of cyclic ethers, including epoxides and sugars, leading to the corresponding alcohols and/or hydrocarbons. The chemical reactivity and selectivity of these ring‐opening catalytic processes are discussed with respect to the type of substrates; the representative catalytic working modes are also described.