PCET-mediated deconstructive cross-coupling of aliphatic alcohols

Abstract

A practical deconstructive arylation of aliphatic alcohols has been developed using a synergistic photoredox proton-coupled electron transfer (PCET) and nickel dual catalytic system. The method efficiently generates alkyl radicals via concerted PCET-mediated β-scission, enabling the formation of C(sp³)–C(sp²) bonds between alcohols and aryl halides. Optimization studies revealed a broad functional group tolerance and high chemoselectivity, with good yields even for challenging tertiary alcohol substrates. Mechanistic insights from transient absorption spectroscopy confirmed the dominance of a PCET pathway for radical generation. This strategy expands the utility of alcohols as alkyl radical precursors in cross-coupling reactions, offering a versatile tool for constructing complex molecular architectures.