Highly enantioselective carbene-catalyzedδ-lactonization via radical relay cross-coupling  

作　　者：Yuhan Liu Jingyang Zhang Gongming Yang Jian Wang 

机构地区：[1]School of Pharmaceutical Sciences,Key Laboratory of Bioorganic Phosphorous Chemistry and Chemical Biology(Ministry of Education),Tsinghua University,Beijing 100084

出　　处：《Chinese Chemical Letters》2025年第1期253-257,共5页中国化学快报(英文版)

基　　金：financial supports for this work are provided by the National Natural Science Foundation of China(Nos.21871160,21672121,22071130)。

摘　　要：An N-heterocyclic carbene(NHC)catalyzed enantioselective cyclisation and trifluoromethylation of olefins with cinnamaldehydes via radical relay cross-coupling in the presence of Togni reagent is reported andδ-lactones tolerated with stereogenic centers atβ-andγ-positions are obtained in moderate to high yields and with high enantioselectivities.Further computational studies explain that the radical crosscoupling step is the key to determining the enantioselectivity.Energy analysis of key transition states and intermediates also provides a reasonable explanation for the difficulty of diastereoselective control.DFT calculations also reveal that the hydrogen-bonding interaction plays a vital role in the promotion of this chemistry.

关 键 词：Carbene organocatalysis Radical relay cross-coupling TRIFLUOROMETHYLATION CYCLISATION δ-Lactone 

分 类 号：O62[理学—有机化学]