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 ...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.展开更多
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)+1 种基金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.
文摘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.
