Transition-Metal-Catalyzed Regioselective Functionalization of Monophosphino-o-Carboranes

Zi-Yang Zhang; Xuepeng Zhang; Jia Yuan; Chang-Duo Yue; Sixuan Meng; Jian Chen; Guang-Ao Yu; Chi-Ming Che

doi:10.1002/chem.201905647

Transition-Metal-Catalyzed Regioselective Functionalization of Monophosphino-o-Carboranes

Chemistry. 2020 Apr 16;26(22):5037-5050. doi: 10.1002/chem.201905647. Epub 2020 Mar 26.

Authors

Zi-Yang Zhang¹, Xuepeng Zhang^{2

3}, Jia Yuan¹, Chang-Duo Yue¹, Sixuan Meng¹, Jian Chen¹, Guang-Ao Yu¹, Chi-Ming Che^{4

5}

Affiliations

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.
² Laboratory of Computational and Drug Design, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen, 518055, P. R. China.
³ School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710119, 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.
⁵ HKU Shenzhen Institute of Research and Innovation, Shenzhen, Guangdong, 518057, P. R. China.

PMID: 32022324
DOI: 10.1002/chem.201905647

Abstract

A facile approach to the synthesis of diaryl- and dialkyl-substituted monophosphino-o-carboranes by rhodium(I)-catalyzed phosphine-directed B^3,6 -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 Li₂ CO₃ as base, respectively. These discoveries provide some simple and efficient approaches to the modification of monophosphino-o-carboranes.

Keywords: B−H activation; alkylation; arylation; carboranes; halogenation; phosphines.

Abstract

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