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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\u2010centered radicals from common alkyl phosphine compounds. We herein demonstrate that this challenge can be overcome by hiring Janus\u2010faced chlorophosphine as the phosphine source that can act as not only a radical precursor to generate phosphine\u2010centered 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\u2010bisphosphines from readily accessible alkenes and chlorophosphines.<\/jats:p>","DOI":"10.1002\/chem.202304109","type":"journal-article","created":{"date-parts":[[2024,2,10]],"date-time":"2024-02-10T07:09:10Z","timestamp":1707548950000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Construction of Bidentate Phosphines Enabled by Photoinduced Reductive Diphosphination of Alkenes"],"prefix":"10.1002","volume":"30","author":[{"given":"Hongchi","family":"Liu","sequence":"first","affiliation":[{"name":"Key Laboratory of Precision and Intelligent Chemistry Department of Chemistry University of Science and Technology of China  Hefei 230026 P. R. China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0108-6542","authenticated-orcid":false,"given":"Hanmin","family":"Huang","sequence":"additional","affiliation":[{"name":"Key Laboratory of Precision and Intelligent Chemistry Department of Chemistry University of Science and Technology of China  Hefei 230026 P. R. China"},{"name":"Key Laboratory of Green and Precise Synthetic Chemistry and Applications Ministry of Education Huaibei Normal University  Huaibei 235000 P. R. 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