CO2-DBU-Triggered Photoredox-Catalyzed Direct α-C-H Alkylation of Alcohols.

An efficient photoinduced and metal-free method for direct α-C-H monoalkylation of alcohols utilizing the CO2-DBU-system as a hydrogen bond acceptor (HBA) catalyst in the presence of water (H2O) is reported. This protocol allows for selective functionalization of alcohols with a broad substrate scope, demonstrating yields up to 88% in 36 examples. Systematic computational analysis using DFT calculations reveals insights into the mechanism by identifying the key intermediates assembled via intermolecular hydrogen bond between DBU-CO2 adduct and alcohol. This strategy opens new avenues for efficient alkylation of ordinary alcohols, offering an environmentally friendly approach to complex molecular synthesis.