Enantioselective Si−H Insertion of Arylvinyldiazoesters Promoted by Rhodium(I)/Diene Complexes

An enantioselective Si−H insertion between α‐arylvinyldiazoesters and silanes has been developed by employing rhodium(I)/chiral diene complex as the catalyst. This protocol offers a catalytic asymmetric approach to various chiral silanes containing α‐arylvinyl functionality at room temperature with good enantiocontrol (89–99% ee). Transformation of the resulting enantiomerically enriched α‐arylvinyl‐α‐silyl esters led to a variety of other valuable building blocks. The deuterium kinetic isotope effect experiments revealed a rhodium(I)‐mediated concerted Si−H insertion mechanism.