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Despite extensive studies, the reaction of SCBs with simple alkenes has only one precedent. Moreover, most reported reactions of SCBs use late transition metals (Pd, Ni, Rh) as catalysts. By contrast, there are no reports of using early transition metals. Herein, we report the first example, to our knowledge, of early\u2010transition\u2010metal\u2010catalyzed reactions of SCBs using earth's second abundant titanium as a catalyst. Notably, orthogonal selectivity was observed. Selective activation of the relatively inert C(sp<jats:sup>3<\/jats:sup>)\u2212Si bond was achieved in the case of benzosilacyclobutenes, a selectivity that has rarely been achieved using other metals. Even for silacyclobutanes with C(sp<jats:sup>3<\/jats:sup>)\u2212Si bonds only, our titanium system also shows complementary selectivity towards late transition metals to give distinct products. Thus, structurally varied SCBs and alkenes were reacted in our system to afford structurally diverse silicon\u2010containing products that are otherwise difficult to obtain using other transition metals.<\/jats:p>","DOI":"10.1002\/anie.202420092","type":"journal-article","created":{"date-parts":[[2024,12,5]],"date-time":"2024-12-05T22:40:29Z","timestamp":1733438429000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Titanium\u2010Catalyzed Reaction of Silacyclobutanes with Alkenes: Mimicking the Reactivity and Reversing the Selectivity Towards Late Transition Metals"],"prefix":"10.1002","volume":"64","author":[{"given":"Yaqiong","family":"Wang","sequence":"first","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 Chinese Academy of Sciences  Lanzhou 730000 P. R. 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