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Herein, we report that an in situ generated copper(I)-substituted silylene undergoes reversible insertion into benzene at room temperature, affording a silepin with a reactive Cu\u2013Si bond. This metal\u2013silicon linkage enables diverse substitutions (H, halogen, alkyl, allyl, allenyl, propargyl) through facile cleavage, offering a mild strategy for benzene ring expansion and functionalization.<\/jats:p>","DOI":"10.1021\/acs.orglett.6c03467","type":"journal-article","created":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T19:15:35Z","timestamp":1788462935000},"page":"11779-11783","source":"Crossref","is-referenced-by-count":1,"title":["Room-Temperature\nC\u2013C Bond Cleavage and Ring\nExpansion of Benzene by a Copper(I)-Substituted Silylene"],"prefix":"10.1021","volume":"28","author":[{"given":"Jiabao","family":"Chang","sequence":"first","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510641"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Cheng","family":"Xu","sequence":"additional","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510641"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4664-8980","authenticated-orcid":true,"given":"Yaofeng","family":"Chen","sequence":"additional","affiliation":[{"name":"South China University of Technology , , ,","place":["Guangzhou, China, 510641"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,3]]},"reference":[{"key":"2026091809424901600_cit1","volume-title":"Arene Chemistry: Reaction\nMechanisms and Methods for Aromatic Compounds","author":"Mortier","year":"2016"},{"key":"2026091809424901600_cit2","doi-asserted-by":"publisher","first-page":"123","DOI":"10.1016\/S0920-5861(00)00612-X","article-title":"Skeletal Isomerization of Alkanes\nand Hydroisomerization of Benzene Over Solid Strong Acids and Their\nBifunctional Catalysts","volume":"66","author":"Watanabe","year":"2001","journal-title":"Catal. 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