Reductive Cross‐Coupling of Alcohol Derivatives with Chlorosilanes via Pyridines‐Promoted Si─Cl Activation

Abstract The development of efficient approaches mediated by silyl radicals for constructing C─Si bonds is of great interest and importance, yet methods to generate these intermediates from readily available chlorosilanes remain scarce. Herein, we report a new strategy for silyl radical generation via pyridines‐promoted reductive Si─Cl activation of chlorosilanes and demonstrate its application in the reductive cross‐coupling with a wide array of benzyl, allyl, and propargyl alcohol derivatives. This protocol offers an efficient and step‐economical route for the synthesis of diverse benzyl‐, allyl‐, and allenylsilanes, featuring broad substrate scope and easy scalability. Mechanistic investigations suggest that the coupling reaction was initiated by the reductive Si─Cl activation of chlorosilanes with magnesium promoted by pyridine derivatives, which generates silyl radicals. These silyl radicals subsequently mediate the deoxygenation of alcohol derivatives to form carbon radicals, culminating in C─Si radical–radical cross‐coupling.