Iron‐Catalyzed Enantioselective Hydrosilylation of <i>α</i> ‐Substituted Vinylsilanes ^†

Comprehensive Summary The first iron‐catalyzed asymmetric hydrosilylation of α‐substituted vinylsilanes is reported. This reaction proceeds with high regio‐ and enantioselectivity, providing an efficient access to enantioenriched chiral vicinal bis(silane)s bearing derivatizable Si–H bonds. Importantly, the localized steric bulky effect in the new designed ligand significantly enhances both yield and enantioselectivity. Furthermore, gram‐scale synthesis could be performed smoothly. The derivatizations of the resulting chiral vicinal bis(silane)s are also demonstrated, furnishing high‐value cyclosiloxane and siloxane.