Iron-Catalyzed Synthesis of Unsymmetrical Disilanes

Disilanes, especially unsymmetrical ones, are among the most important organosilane reagents in organic synthesis and possess broad prospects in advanced materials. Despite the development of some synthetic approaches, the preparation of modifiable unsymmetrical disilanes remains a significant challenge, thereby hindering further functional exploration. Here, we report a combined ligand design strategy that enabled the development of a novel iron catalyst, achieving an unprecedented iron-catalyzed hydrodisilylation of alkynes with dihydrodisilanes. This method facilitates the highly chemo-, regio-, and stereoselective syntheses of diverse unsymmetrical vinyldisilanes with Si-H bonds. Mechanistic studies and density functional theory calculations reveal that this method provides a novel model for selective disilane functionalization that fully preserves Si-Si bonds, overcoming the limitation of low-valent transition metal catalysis, which typically cleaves Si-Si bonds. The straightforward, scalable, and readily accessible protocol exhibits an exceptional turnover frequency, good functional group tolerance, and broad substrate scope. Notably, the resulting functionalized vinyldisilanes exhibit versatile reactivity, enabling the construction of various privileged scaffolds via site-specific cleavage.