Lyu Hairong, Xie Zuowei
Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, NT, China.
Chem Commun (Camb). 2022 Jul 26;58(60):8392-8395. doi: 10.1039/d2cc02852b.
A unique approach to vertex-selective catalytic B-H amination at either the B(3)- or B(4)-position in -carboranes has been developed. Using different transition metal catalysts, dehydrogenative BH/NH cross-coupling of -carboranes and free amines has been achieved, leading to a wide variety of cage B(3)- or B(4)-aminated -carboranes in moderate to high yields with excellent regioselectivity, where carboranyl carboxylic acids and amines can serve as competent coupling partners without any pre-functionalization. The isolation and structural identification of a key intermediate provide an insight into the reaction mechanism in the catalytic B(4)-H amination.
已开发出一种独特的方法，用于在碳硼烷的B(3)-或B(4)-位进行顶点选择性催化B-H胺化反应。使用不同的过渡金属催化剂，实现了碳硼烷与游离胺的脱氢BH/NH交叉偶联反应，以中等到高的产率和优异的区域选择性得到了多种笼状B(3)-或B(4)-胺化碳硼烷，其中碳硼烷基羧酸和胺无需任何预官能化即可作为合适的偶联伙伴。关键中间体的分离和结构鉴定为催化B(4)-H胺化反应的机理提供了深入了解。
