Lin En-Ze, Zhao Wei, Shi Jun-Kai, Sun Yu-Wen, Xiong Xianrui, Qi Xiaotian, Sun Xin, Li Bi-Jie
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University, Beijing, 100084, China.
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei, 430072, China.
Angew Chem Int Ed Engl. 2025 Jun 24;64(26):e202501641. doi: 10.1002/anie.202501641. Epub 2025 Apr 26.
Transition metal-catalyzed direct addition of (hetero)aryl C─H bond to an alkene provides an expedited route to construct benzylic stereocenter from readily available arene and alkene feedstocks with complete atom-economy. However, creation of more than one stereocenter through enantioselective C─H (hetero)arylation remains a challenging goal. Here we report an iridium-catalyzed desymmetric hydroheteroarylation of cyclopentenes to construct 1,3-nonadjacent stereocenters. A series of heteroaryl C─H bonds were cleaved site-selectively and added regio- and enantioselectively to an unactivated alkene containing an amide coordinating group, delivering valuable enantioenriched cyclopentane scaffolds containing 1,3-tertiary-tertiary or 1,3-quaternary-tertiary stereocenters with exclusive diastereoselectivity and excellent enantioselectivity.
过渡金属催化的（杂）芳基C─H键与烯烃的直接加成反应为从易得的芳烃和烯烃原料出发，以完全原子经济性构建苄基立体中心提供了一条快捷途径。然而，通过对映选择性C─H（杂）芳基化反应创建多个立体中心仍然是一个具有挑战性的目标。在此，我们报道了铱催化的环戊烯的去对称氢杂芳基化反应，用于构建1,3-非相邻立体中心。一系列杂芳基C─H键被位点选择性地裂解，并区域和对映选择性地加成到含有酰胺配位基团的未活化烯烃上，以专一的非对映选择性和优异的对映选择性提供了含有1,3-叔-叔或1,3-季-叔立体中心的有价值的对映体富集的环戊烷骨架。
