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However, owing to the presence of multiple identical C(sp<jats:sup>2<\/jats:sup>)\u2010H sites, this protocol often suffers from low reactivity and selectivity issues, especially for the regioselective synthesis of 1,3\u2010difunctionalized metallocenes. Herein, an efficient iridium\u2010catalyzed meta\u2010selective C\u2013H borylation of metallocenes is reported. With no need of preinstalled directing groups, this approach enables a rapid synthesis of various boronic esters based on benzoferrocenes, ferrocenes, ruthenocene, and related half sandwich complex. A broad range of electron\u2010deficient and \u2010rich functional groups are all compatible with the process. Notably, C\u2013H borylation of benzoferrocenes takes place exclusively at the benzene ring, which is likely ascribed to the shielding effect of pentamethylcyclopentadiene. The synthetic utility is further demonstrated by easy scalability to gram quantities, the conversion of boron to heteroatoms including N<jats:sub>3<\/jats:sub>, SePh, and OAc, as well as diverse cross\u2010coupling reactions.<\/jats:p>","DOI":"10.1002\/advs.202304672","type":"journal-article","created":{"date-parts":[[2023,8,26]],"date-time":"2023-08-26T11:28:34Z","timestamp":1693049314000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Catalytic Undirected Meta\u2010Selective C\u2013H Borylation of Metallocenes"],"prefix":"10.1002","volume":"10","author":[{"given":"Hao","family":"Zheng","sequence":"first","affiliation":[{"name":"Dalian Institute of Chemical Physics Chinese Academy of Sciences  Dalian 116023 P. R. China"},{"name":"University of Chinese Academy of Sciences  Beijing 100049 P. R. 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