Earth-Abundant Manganese Catalysts for Dehydrogenative Coupling of Alcohols and Silanols with Hydrosilanes

Abstract The development of catalysts and/or simple systems based on earth-abundant metals that enable the selective synthesis of siloxanes and alkoxysilanes while generating valuable hydrogen as the sole byproduct remains a major challenge in catalysis. Herein, we report a mild, scalable, and chemoselective cross-dehydrogenative functionalization protocol for the construction of Si–O–Si and Si–O–C motifs. The method relies on the dehydrogenative coupling of hydrosilanes with silanols or alcohols catalyzed by manganese complexes and simple manganese chloride, enabling efficient Si–O bond formation under operationally straightforward conditions. This transformation expands the synthetic tool box of organosilicon chemistry by introducing an earth-abundant metal catalyst bearing aminophosphine-type ligands and provides a practical approach to the synthesis of siloxanes and silyl ethers with broad functional group tolerance.