A Comprehensive Review of Intramolecular Hydrosilylation of Alkynes and Alkenes

Abstract Hydrosilylation reactions of alkenes and alkynes have been widely used to form compounds containing a silicon atom. Applied in intramolecular version, these processes enable the formation of silylated heterocycles, which are important building blocks in the synthesis of drugs, fragrances or materials. This review gives an overview of reports on the enhancement of intramolecular reactions, from noble metals to other transition metals, via other type of activation. The regio‐ and stereochemical aspects of these various processes are also reported, in correlation with plausible Chalk–Harrod, modified Chalk–Harrod, Crabtree–Ojima, or Glaser–Tilley mechanisms.