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.

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 compared to analogous deoxygenative electrocarboxylation.

Single-atom catalysts (SACs) hold the potential to combine the benefits of both heterogeneous and homogeneous catalysis. In this issue of Chem, Beller and co-workers demonstrate the selective insertion of transient copper carbenes into diverse X‒H (X = C, N, O, S) bonds with excellent functional-group tolerance by using a porous Al2O3-supported SAC.