Nickel-Catalyzed C(sp³)–C(sp³) Coupling of Cyclopropanols via α-Bimetalloid Radicals: Access to γ-Carbonyl <i>gem</i>-Bis(boronates) and <i>gem</i>-Silylboronate Esters

Herein, we disclose an efficient nickel-catalyzed C(sp³)-C(sp³) coupling reaction of ambiphilic reagents with cyclopropanols, enabling direct access to a range of synthetically valuable γ-carbonyl <i>gem</i>-diboronates and γ-carbonyl <i>gem</i>-silylboronate esters in good yields. This method shows broad substrate scope and excellent functional group tolerance for cyclopropanols. Mechanistic studies indicate the involvement of α-bimetalloid radicals, and the resulting Bpin groups in products offer versatile handles for further derivatization.