区域选择性、立体选择性和对映选择性的原位及迁移脱氟烯烃交叉偶联反应，用于合成高度官能化的单氟烯烃。
Regio-, stereo-, and enantioselective ipso- and migratory defluorinative olefin cross-coupling to access highly functionalized monofluoroalkenes.
作者信息
Zeng Daning, Liu Zihao, Huang Guoce, Wang You, Zhu Shaolin
机构信息
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, 453007, China.
出版信息
Nat Commun. 2024 Sep 2;15(1):7645. doi: 10.1038/s41467-024-52054-6.
Monofluoroalkenes serve as nonhydrolyzable mimetics of amides and are frequently encountered in drug candidates. Herein we report a regio-, enantio-, and stereoselective NiH-catalyzed ipso- and migratory defluorinative olefin cross-coupling employing readily available olefins and gem-difluoroalkenes under mild conditions. This approach enables the efficient synthesis of a broad array of structurally diverse monofluoroalkenes bearing a tertiary allylic stereogenic center. Mechanistically, the challenging migratory defluorinative olefin cross-coupling process is successfully realized through a ligand relay catalytic strategy, enabling the formal C(sp)-H/C(sp)-F activation with high levels of regio-, stereo-, and enantiocontrol.
单氟烯烃作为酰胺的不可水解模拟物，在候选药物中经常出现。在此，我们报道了一种在温和条件下，使用易得的烯烃和偕二氟烯烃，通过区域、对映体和立体选择性的NiH催化原位和迁移脱氟烯烃交叉偶联反应。该方法能够高效合成一系列具有叔烯丙基立体中心、结构多样的单氟烯烃。从机理上讲，具有挑战性的迁移脱氟烯烃交叉偶联过程通过配体接力催化策略得以成功实现，从而实现了具有高水平区域、立体和对映体控制的形式上的C(sp)-H/C(sp)-F活化。
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