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This method is established through reductive C\u2212Si coupling of chlorohydrosilanes via unconventional Si\u2212Cl cleavage. The reaction offers access to aryl\u2010 and alkenylhydrosilanes with a scope that is complementary to those of the established methods. Electron\u2010rich, electron\u2010poor, and <jats:italic>ortho<\/jats:italic>\u2010\/<jats:italic>meta<\/jats:italic>\u2010\/<jats:italic>para<\/jats:italic>\u2010substituted (hetero)aryl electrophiles, as well as cyclic and acyclic alkenyl electrophiles, were coupled successfully. Functionalities, including Grignard\u2010sensitive groups (e.g., primary amine, amide, phenol, ketone, ester, and free indole), acid\u2010sensitive groups (e.g., ketal and THP protection), alkyl\u2010Cl, pyridine, furan, thiophene, Ar\u2010Bpin, and Ar\u2010SiMe<jats:sub>3<\/jats:sub>, were tolerated. Gram\u2010scale reaction, incorporation of \u2010Si(H)R<jats:sub>2<\/jats:sub> into complex biologically active molecules, and derivatization of formed organohydrosilanes are demonstrated.<\/jats:p>","DOI":"10.1002\/anie.202200215","type":"journal-article","created":{"date-parts":[[2022,3,8]],"date-time":"2022-03-08T09:13:03Z","timestamp":1646730783000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":88,"title":["Nickel\u2010Catalyzed Reductive C(sp<sup>2<\/sup>)\u2212Si Coupling of Chlorohydrosilanes via Si\u2212Cl Cleavage"],"prefix":"10.1002","volume":"61","author":[{"given":"Zhen\u2010Zhen","family":"Zhao","sequence":"first","affiliation":[{"name":"State Key Laboratory of Applied Organic Chemistry (SKLAOC) College of Chemistry and Chemical Engineering Lanzhou University  222 South Tianshui Road Lanzhou 730000 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaobo","family":"Pang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Applied Organic Chemistry (SKLAOC) College of Chemistry and Chemical Engineering Lanzhou University  222 South Tianshui Road Lanzhou 730000 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiao\u2010Xue","family":"Wei","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Applied Organic Chemistry (SKLAOC) College of Chemistry and Chemical Engineering Lanzhou University  222 South Tianshui Road Lanzhou 730000 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xue\u2010Yuan","family":"Liu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Applied Organic Chemistry (SKLAOC) College of Chemistry and Chemical Engineering Lanzhou University  222 South Tianshui Road Lanzhou 730000 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Our studies revealed that when Me(pent-4-en-1-yl)Si(Ph)\u2212H treatment with DTBP (0.5\u2005equiv) in benzene at 145\u2009\u00b0C a classic radical condition the formed silyl radical could readily cyclize with an alkene to form a six-membered product in 45\u2009% yield (Scheme\u2005S1). 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