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Transition-Metal-Catalyzed Regioselective Functionalization of Monophosphino-o-Carboranes
Authors:Zi-Yang Zhang  Dr Xuepeng Zhang  Dr Jia Yuan  Chang-Duo Yue  Dr Sixuan Meng  Dr Jian Chen  Prof Guang-Ao Yu  Prof Chi-Ming Che
Institution:1. Department Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, Chemical Biology Center, College of Chemistry, Central China Normal University, Wuhan, 430079 P. R. China

These authors contributed equally to this work.;2. Laboratory of Computational and Drug Design, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen, 518055 P. R. China

School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119 P. R. China

These authors contributed equally to this work.;3. Department Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, Chemical Biology Center, College of Chemistry, Central China Normal University, Wuhan, 430079 P. R. China;4. State Key Laboratory of Synthetic Chemistry and, Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China

Abstract:A facile approach to the synthesis of diaryl- and dialkyl-substituted monophosphino-o-carboranes by rhodium(I)-catalyzed phosphine-directed B3,6−H activation has been developed for the first time. Upon switching rhodium(I) to palladium(II), C-arylated and B6-halogenated products were obtained by using tBuOLi and Li2CO3 as base, respectively. These discoveries provide some simple and efficient approaches to the modification of monophosphino-o-carboranes.
Keywords:alkylation  arylation  B−H activation  carboranes  halogenation  phosphines
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