Selective Electrochemical Hydrolysis of Hydrosilanes to Silanols via Anodically Generated Silyl Cations

The first electrochemical hydrolysis of hydrosilanes to silanols under mild and neutral reaction conditions is reported. The practical protocol employs commercially available and cheap NHPI as a hydrogen‐atom transfer (HAT) mediator and operates at room temperature with high selectivity, leading to various valuable silanols in moderate to good yields. Notably, this electrochemical method exhibits a broad substrate scope and high functional‐group compatibility, and it is applicable to late‐stage functionalization of complex molecules. Preliminary mechanistic studies suggest that the reaction appears to proceed through a nucleophilic substitution reaction of an electrogenerated silyl cation with H2O. A practical electrochemical method for selective hydrolysis of hydrosilanes to furnish diverse silanols has been achieved. These reactions occur with high chemoselectivity and functional‐group tolerance under mild and neutral reaction conditions. The addition of NHPI as a HAT mediator is crucial for promoting the generation of silyl cation species.