Phosphine-Catalyzed Z-Selective Carbofluorination of Alkynoates Bearing an N-Heteroarene Unit
Phosphine-Catalyzed Z-Selective Carbofluorination of Alkynoates Bearing an N-Heteroarene Unit
复制标题
膦催化的带有 N-杂芳烃单元的炔酸酯的 Z 选择性碳氟化
DOI：
10.1055/a-1948-3234
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Takenaka Namiki
中科院分区：
文献类型：
--
作者：
Tobisu Mamoru;Fujimoto Hayato;Yamamura Shisato;Takenaka Namiki
本文报道了以酰氟为双功能试剂，膦催化含N-杂芳烃单元的炔酸酯的Z-选择性羰基化反应。该反应通过五配位氟膦（V）中间体进行，导致通过配体偶联过程形成C-F键。Z-异构体的选择性归因于N-杂芳烃的孤对电子与羰基的π* 轨道之间的轨道相互作用对Z-异构体的热力学稳定。
We report herein on the phosphine-catalyzedZ-selective carbofluorination of alkynoates bearing an N-heteroarene unit, by using acyl fluorides as bifunctional reagents. This reaction proceeds through a pentacoordinate fluorophosphorane(V) intermediate, resulting in the formation of a C–F bond by a ligand coupling process. TheZ-selectivity is attributed to the thermodynamic stabilization of aZ-isomer by orbital interactions between lone pair electrons of an N-heteroarene and the π* orbital of a carbonyl group.