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Revealing Silylation of C(sp2)/C(sp3)–H Bonds in Arylphosphines by Ruthenium Catalysis
Authors:Dr Jian Wen  Dr Ben Dong  Jinjun Zhu  Dr Yue Zhao  Prof Dr Zhuangzhi Shi
Institution:1. State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093 China

These authors contributed equally to this work.;2. State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093 China

Abstract:The first aromatic C−H silylation between arylphosphines and hydrosilanes enabled by a ruthenium complex has been developed. The excellent ortho-selectivity results from a four-membered metallacyclic intermediate involving phosphorus chelation. The developed system can be extended to the benzylic C−H silylation of arylphosphines. Diverse silylated arylphosphines are produced, exhibiting broad functional group compatibility. Further functionalization of the products under mild conditions renders the formed compounds useful building blocks.
Keywords:C−H activation  coordination  phosphorus  silylation  site selectivity
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