Scholarlink

<p>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.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Site- and enantioselective B−H functionalization of carboranes

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2025年5月6日

查看全文
  • Kyungsup Lee,
  • Gisela A. González-Montiel,
  • Hyeonsik Eom,
  • Tae Hyeon Kim,
  • Hee Chan Noh,
  • Abdikani Omar Farah,
  • Henry R. Wise,
  • Dongwook Kim,
  • Paul Ha-Yeon Cheong,
  • Phil Ho Lee

摘要

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.