A chronicle review: Regioselective synthesis of trifluoromethyl group containing allylic amines using palladium-catalyzed allylic amination pathway

Abstract

Palladium-catalyzed regioselective allylic amination of the α-trifluoromethyl group-substituted allyl acetate has been accomplished using Pd(OAc)2/DPPE and [Pd(π-allyl)(cod)]BF4/DPPF as catalysts. The selective formation of the γ-product was attained by the use of Pd(OAc)2/DPPE, while the α-product was obtained in the presence of [Pd(π-allyl)(cod)]BF4/DPPF. We also succeeded in synthesizing optically active allylic amines using Pd(OAc)2/DPPE and [Pd(π-allyl)(cod)]BF4/BINAP began from optically active trifluoromethyl-substituted allyl acetate. Furthermore, we established that kinetic resolution of two types of allylic amines was possible using enantioselective isomerization by the [Pd(π-allyl)(cod)]BF4/(S)-BINAP catalyst.