The diphosphination of alkenes through a radical pathway offers a promising approach for the rapid construction of aryl bisphosphines. However, such a synthetic strategy has not been successfully applied to the preparation of alkyl bisphosphines, partially due to the difficulties in the generation of phosphorus-centered radicals from common alkyl phosphine compounds. We herein demonstrate that this challenge can be overcome by hiring Janus-faced chlorophosphine as the phosphine source that can act as not only a radical precursor to generate phosphine-centered radicals but also a radicalphile to capture alkyl radicals. With this novel strategy, a photocatalyzed reductive diphosphination reaction has been established, allowing for a straightforward synthesis of both aryl and alkyl 1,2-bisphosphines from readily accessible alkenes and chlorophosphines.
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