Lyu Hairong, Quan Yangjian, Xie Zuowei
Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong, P.R. China.
Chemistry. 2017 Oct 20;23(59):14866-14871. doi: 10.1002/chem.201703006. Epub 2017 Sep 21.
Transition metal catalyzed, regioselective carborane-cage B(4)-H iodination, bromination, and chlorination as well as B(4,5)-H diiodination were achieved by using NXS (X=I, Br), FeCl , or IOAc as the halogenating agent, respectively. A series of previously inaccessible B(4)-halogenated o-carboranes were synthesized in a simple one-pot process, and proved to be valuable synthons for the functionalization of carboranes. Mono- and di-selectivity can be controlled by in situ removal of the carboxy directing group. The resultant 4-I-o-C B H can serve as a versatile feedstock for the construction of cage B-C(sp ), B-C(sp), B-O, and B-N bonds.
通过分别使用NXS（X = I，Br）、FeCl₃或IOAc作为卤化剂，实现了过渡金属催化的区域选择性碳硼烷笼状结构B(4)-H的碘化、溴化和氯化以及B(4,5)-H的二碘化。一系列以前无法获得的B(4)-卤代邻碳硼烷通过简单的一锅法合成，并被证明是用于碳硼烷功能化的有价值的合成子。单选择性和双选择性可以通过原位去除羧基导向基团来控制。所得的4-I-o-C₂B₁₀H₁₁可作为构建笼状B-C(sp³)、B-C(sp)、B-O和B-N键的通用原料。
