Rh-Catalyzed Decarbonylative Cross-Coupling between o-Carboranes and Twisted Amides: A Regioselective,Additive-Free,and Concise Late-Stage Carboranylation |
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| Authors: | Dr. Chun-Xiao Li Qian Ning Wenxuan Zhao Hou-Ji Cao Yi-Ping Wang Prof. Dr. Hong Yan Prof. Dr. Chang-Sheng Lu Prof. Dr. Yong Liang |
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| Affiliation: | State Key Laboratory of Coordination Chemistry, Jiangsu Key, Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023 P. R. China |
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| Abstract: | The convenient cross-coupling of sp2 or sp3 carbons with a specific boron vertex on carborane cage represents significant synthetic values and insurmountable challenges. In this work, we report an Rh-catalyzed reaction between o-carborane and N-acyl-glutarimides to construct various Bcage−C bonds. Under the optimized condition, the removable imine directing group (DG) leads to B(3)− or B(3,6)−C couplings, while the pyridyl DG leads to B(3,5)−Ar coupling. In particular, an unexpected rearrangement of amide reagent is observed in pyridyl directed B(4)−C(sp3) formation. This scalable protocol has many advantages, including easy access, the use of cheap and widely available coupling agents, no requirement of an external ligand, base or oxidant, high efficiency, and a broad substrate scope. Leveraging the RhI dimer and twisted amides, this method enables straightforward access to diversely substituted and therapeutically important carborane derivatives at boron site, and provides a highly valuable vista for carborane-based drug screening. |
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| Keywords: | B−H activation carboranes C−N activation late stage rhodium |
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