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Metal-Free Oxidative B-N Coupling of nido-Carborane with N-Heterocycles
Zhongming Yang1, Weijia Zhao1, Wei Liu1
1State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
Abstract:
A general method for the oxidative substitution of nido-carborane (7,8-C2 B9 H12 - ) with N-heterocycles has been developed by using 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) as an oxidant. This metal-free B-N coupling strategy, in both inter- and intramolecular fashions, gave rise to a wide array of charge-compensated, boron-substituted nido-carboranes in high yields (up to 97 %) with excellent functional-group tolerance under mild reaction conditions. The reaction mechanism was investigated by density-functional theory (DFT) calculations. A successive single-electron transfer (SET), B-H hydrogen-atom transfer (HAT), and nucleophilic attack pathway is proposed. This method provides a new approach to nitrogen-containing carboranes with potential applications in medicine and materials.
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