Rhodium-Catalyzed Asymmetric Trifluoromethoxylation of Racemic Allylic Trichloroacetimidates  

作　　者：Liyan Wang Yafeng Si Yu-Xin Luan Pingping Tang 

机构地区：[1]State Key Laboratory and Institute of Elemento-Organic Chemistry,College of Chemistry,Nankai University,Tianjin 300071

出　　处：《CCS Chemistry》2024年第8期1885-1894,共10页中国化学会会刊（英文）

基　　金：supported by the National Key Research and Development Program of China(grant no.2021YFF0701700);the National Natural Science Foundation of China(grant nos.21925105,92156001,and 22101141);the Natural Science Foundation of Tianjin(grant no.18JCJQJC47000);the Haihe Laboratory of Sustainable Chemical Transformations,and the Fundamental Research Funds for the Central Universities.

摘　　要：A rhodium/diene catalyzed asymmetric allylic trifluoromethoxylation reaction is reported,which afforded chiral trifluoromethoxylated allylic compounds in 52%–97%yields with up to 97%enantiomeric excess.These are the first examples of asymmetric allylic trifluoromethoxylation.The reactions proceed via a dynamic kinetic process that allowed for the use of racemic allylic trichloroacetimidates as substrates.Density functional theory calculations showed that the formation of the C–OCF_(3)bond occurs via outer-sphere nucleophilic attack.Importantly,the presence of the allylic group in the products enabled them to be converted into a diverse array of optically active trifluoromethylated molecules that are otherwise difficult to access.

关 键 词：asymmetric trifluoromethoxylation trifluoromethyl arylsulfonates rhodium trichloroacetimidates chiral diene ligand 

分 类 号：O62[理学—有机化学]