A Nickel-Catalyzed Method for Csp ³ –P(III) Bond Formation: Efficient Transformation of Chlorophosphines with Alkyl Bromides

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.