Lee Kyungsup, González-Montiel Gisela A, Eom Hyeonsik, Kim Tae Hyeon, Noh Hee Chan, Farah Abdikani Omar, Wise Henry R, Kim Dongwook, Cheong Paul Ha-Yeon, Lee Phil Ho
Department of Chemistry, Kangwon National University, Chuncheon, 24341, Republic of Korea.
Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, OR, 97331-2145, USA.
Nat Commun. 2025 May 6;16(1):4182. doi: 10.1038/s41467-025-59410-0.
Functionalization of carboranes, icosahedral boron-carbon molecular clusters, is of great interest as they have wide applications in medicinal and materials chemistry. Thus, site- and enantioselective synthesis of carboranes requires complete control of the reaction. Herein, we describe the asymmetric Rh(II)-catalyzed insertion reactions of carbenes into cage B-H bond of carboranes. This reaction thereby generates carboranes possessing a carbon-stereocenter adjacent to cage boron of the carborane, in excellent site- and enantioselectivity under mild reaction conditions. The fully computed transition structures of Rh(II)-catalyzed carbene insertion process through density functional theory are reported. These B-H insertion transition structures, in conjunction with topographical proximity surfaces analyses, visually reveal the region between the carborane and the phthalimide ligands responsible for the selectivities of this reaction.
碳硼烷（二十面体硼 - 碳分子簇）的官能团化备受关注，因为它们在药物化学和材料化学中有广泛应用。因此，碳硼烷的位点和对映选择性合成需要对反应进行完全控制。在此，我们描述了铑（II）催化的卡宾对碳硼烷笼状B - H键的不对称插入反应。该反应由此在温和的反应条件下以优异的位点和对映选择性生成了在碳硼烷笼状硼附近具有碳立体中心的碳硼烷。报道了通过密度泛函理论对铑（II）催化的卡宾插入过程进行的全计算过渡结构。这些B - H插入过渡结构，结合拓扑接近表面分析，直观地揭示了碳硼烷与邻苯二甲酰亚胺配体之间负责该反应选择性的区域。
