A nickel-catalyzed reductive cross-coupling enables efficient Csp3–P(III) bond formation from unactivated alkyl bromides and chlorophosphines. This strategy features a broad substrate scope, allowing the direct phosphorylation of primary, secondary, and tertiary alkyl bromides. In contrast to conventional methods, this approach operates without preformed air-sensitive organometallic reagents or multistep-synthesized phosphorus sources, while overcoming key challenges such as the low reactivity of alkyl substrates, competitive β-hydride elimination, and the high electrophilicity and hydrolytic susceptibility of chlorophosphines. A plausible reaction mechanism is proposed. This method provides a streamlined and versatile route to diverse alkylphosphine libraries with the potential for advancing the applications of organophosphorus compounds in catalysis, materials science, and biology.
Pan et al. (Tue,) studied this question.