Lai Xiao-Li, Xu Hai-Chao
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.
J Am Chem Soc. 2023 Aug 30;145(34):18753-18759. doi: 10.1021/jacs.3c07146. Epub 2023 Aug 15.
The asymmetric difunctionalization of alkenes, a method transforming readily accessible alkenes into enantioenriched chiral structures of high value, has long been a focal point of organic synthesis. Despite tremendous efforts in this domain, it remains a considerable challenge to devise enantioselective oxidative dicarbofunctionalization of alkenes, even though these transformations can utilize stable and unfunctionalized functional group donors. In this context, we report herein a photoelectrocatalytic method for the enantioselective heteroarylcyanation of aryl alkenes, which employs unfunctionalized heteroarenes through C-H functionalization. The photoelectrochemical asymmetric catalysis (PEAC) method combines photoredox catalysis and asymmetric electrocatalysis to facilitate the formation of two C-C bonds operating via hydrogen (H) evolution and obviating the need for external chemical oxidants.
烯烃的不对称双官能团化是一种将易于获得的烯烃转化为具有高价值的对映体富集手性结构的方法，长期以来一直是有机合成的焦点。尽管在该领域付出了巨大努力，但设计烯烃的对映选择性氧化双碳官能团化仍然是一项相当大的挑战，即使这些转化可以利用稳定且未官能团化的官能团供体。在此背景下，我们在此报告一种用于芳基烯烃对映选择性杂芳基氰化的光电催化方法，该方法通过C-H官能团化使用未官能团化的杂芳烃。光电化学不对称催化（PEAC）方法结合了光氧化还原催化和不对称电催化，以促进通过析氢形成两个C-C键，并且无需外部化学氧化剂。
