Nickel(0)-CatalyzedStereospecific and EnantioselectiveRing-Opening Hydrosilylation of Methylenecyclopropanes to Access (<i>E</i>)‑Homoallylsilanes

Homoallylsilanes are versatile organosilicon compounds with broad utility in synthetic and materials chemistry. However, existing methods for their synthesis remain limited, often restricted to conjugated diene hydrosilylation. In this study, we introduce a nickel(0)-catalyzed stereospecific hydrosilylation of methylenecyclopropanes (MCPs), enabling the efficient synthesis of (<i>E</i>)-homoallylsilanes with diverse hydrosilanes. This catalytic system displays high stereoselectivity and functional group tolerance, producing exclusively linear (<i>E</i>)-homoallylsilanes, in contrast to previously reported base-metal-catalyzed MCPs hydrosilylation methods. Additionally, by employing TADDOL-based chiral phosphoramidites, we extend this method to an asymmetric protocol that enables enantioselective synthesis of silicon-stereogenic (<i>E</i>)-homoallylsilanes in high yields and enantioselectivity. This work represents a real advancement, providing a broadly applicable route to enantioenriched silicon-stereogenic homoallylsilanes, compounds previously inaccessible through conventional synthetic methods.