Regiodivergent Hydrosilylation of Polar Enynes to Synthesize Site‐Specific Silyl‐Substituted Dienes

Herein, we present catalyst-regulated switchable site-selective hydrosilylation of enynes, which are suitable for a wide range of alkyl and aryl substituted polar enynes and exhibit excellent functional group compatibility. Under the optimized conditions, silyl groups can be precisely installed at various positions of 1,3-dienes.  While a- and γ-silylation products were obtained under platinum-catalytic systems, b-silylation products were delivered with [Cp*RuCl]4 as catalyst. This process leads to the formation of 1,3-dienoates with diverse substitutions, which would pose challenges with other methodologies.