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However, this mature process has the intrinsic defects of step efficiency and regioselectivity. Herein, we report a nickel\u2010catalyzed divergent, one\u2010step double hydrocyanation of 1,3\u2010butadiene to produce either adiponitrile or 2\u2010methylglutaronitrile in high regioselectivity. The key to this success lies in the highly tunable binding pockets of the bidentate phosphite ligands, which creates a geometrically defined coordination space around the nickel center. The first hydrocyanation that produces either the linear or branched alkenyl nitrile was identified as the selectivity\u2010determining step. Organometallic studies confirm the formation of well\u2010defined diphosphite nickel diene complexes in solution, and the role of ligands in dictating regioselectivity was further rationalized by DFT computations. This result provides the first example of a highly selective nickel\u2010catalyzed synthesis of adiponitrile and 2\u2010methylglutaronitrile from butadiene, and it also represents a high\u2010level of catalyst\u2010controlled regioselectivity via the fine\u2010tuning of ligand pocket geometry.<\/jats:p>","DOI":"10.1002\/anie.202422337","type":"journal-article","created":{"date-parts":[[2024,12,23]],"date-time":"2024-12-23T16:02:52Z","timestamp":1734969772000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["One\u2010Step Process for the Regiodivergent Double Hydrocyanation of 1,3\u2010Butadiene"],"prefix":"10.1002","volume":"64","author":[{"given":"Jinguo","family":"Long","sequence":"first","affiliation":[{"name":"Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education Key Laboratory of Organosilicon Material Technology of Zhejiang Province College of Material, Chemistry and Chemical Engineering Hangzhou Normal University  2318 Yuhangtang Road Hangzhou 311121 P. 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China"},{"name":"Warshel Institute for Computational Biology School of Medicine The Chinese University of Hong Kong  Shenzhen 518172 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hongyu","family":"Zhong","sequence":"additional","affiliation":[{"name":"Laboratorium f\u00fcr Organische Chemie ETH Z\u00fcrich  Vladimir-Prelog-Weg 3 8093 Z\u00fcrich Switzerland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mingdong","family":"Jiao","sequence":"additional","affiliation":[{"name":"Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education Key Laboratory of Organosilicon Material Technology of Zhejiang Province College of Material, Chemistry and Chemical Engineering Hangzhou Normal University  2318 Yuhangtang Road Hangzhou 311121 P. R. China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Bill","family":"Morandi","sequence":"additional","affiliation":[{"name":"Laboratorium f\u00fcr Organische Chemie ETH Z\u00fcrich  Vladimir-Prelog-Weg 3 8093 Z\u00fcrich Switzerland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Lin","family":"He","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization State Key Laboratory for Oxo Synthesis and Selective Oxidation Lanzhou Institute of Chemical Physics (LICP) Chinese Academy of Sciences  Lanzhou 730000 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Gui\u2010Juan","family":"Cheng","sequence":"additional","affiliation":[{"name":"Warshel Institute for Computational Biology School of Medicine The Chinese University of Hong Kong  Shenzhen 518172 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3471-8171","authenticated-orcid":false,"given":"Xianjie","family":"Fang","sequence":"additional","affiliation":[{"name":"Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education Key Laboratory of Organosilicon Material Technology of Zhejiang Province College of Material, Chemistry and Chemical Engineering Hangzhou Normal University  2318 Yuhangtang Road Hangzhou 311121 P. 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