Kang Shuyu, Lv Jiahang, Wang Tianhang, Wu Bingcheng, Wang Minyan, Shi Zhuangzhi
State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu, China.
School of Chemistry and Materials Science, Nanjing Normal University, Nanjing, Jiangsu, China.
Nat Commun. 2024 Aug 27;15(1):7380. doi: 10.1038/s41467-024-51484-6.
Recent strides in C-H borylation have significantly expanded our toolkit for the preparation of organoboronates. Nevertheless, avenues alternative to obtain these compounds via σ-C-C cleavage, thereby facilitating molecular scaffold editing, remain scarce. Several methodologies have been proposed for hydroboration of cyclopropanes by activating C-C bonds, conventionally relying on noble and hazardous metal catalysts to control reaction outcomes. Here, we present a strategy for crafting stereochemically precise γ-borylenamides through ring-opening of cyclopropanes avoiding any metallic entities. Boryl species, generated through a ternary reaction with BCl, cyclopropanes, and a tertiary amine, selectively undergo C-C bond eliminative borylation under the directing of N-acyl group, thereby ensuring enhanced selectivity and efficiency along the reaction pathway. Such inherently stereoconvergent approach accommodates precursors of diverse geometries, including cis/trans isomeric blends.
近年来，碳-氢键硼化领域取得的进展显著扩展了我们制备有机硼酸酯的工具集。然而，通过σ-C-C键裂解来获得这些化合物从而促进分子骨架编辑的替代途径仍然很少。已经提出了几种通过活化C-C键对环丙烷进行硼氢化的方法，传统上依赖于贵金属和危险金属催化剂来控制反应结果。在此，我们提出了一种通过环丙烷开环制备立体化学精确的γ-硼基烯酰胺的策略，该策略无需任何金属实体。通过与BCl、环丙烷和叔胺的三元反应生成的硼基物种，在N-酰基的导向下选择性地进行C-C键消除硼化反应，从而确保反应过程具有更高的选择性和效率。这种固有的立体收敛方法适用于各种几何形状的前体，包括顺式/反式异构体混合物。
