Electrochemical Deoxygenative Silylation of Alcohols

Abstract Alcohols are highly common organic compounds but remain scarce as alkyl donors in synthetic procedures. Here, we describe an electrochemical procedure for their deoxygenative cross‐electrophile coupling with hydrosilanes, furnishing organosilane products in good to excellent yields. Mechanistic studies provide insights into the operating pathways of this semi‐paired electrolytic transformation, suggesting that silyl ethers are likely reaction intermediates. Furthermore, a unified mechanistic proposal is presented that accounts for observed reactivity differences with analogous deoxygenative electrocarboxylation.