Switchable Selectivity in the Annulation of o‐Trifluoroacetylanilines and Activated Terminal Alkynes Based on Transition Metal and Phosphine Catalysis

In this work, we have developed selective methods for the synthesis of quinoline‐2‐carboxylates and quinoline‐3‐carboxylates as well as (indolin‐2‐ylidene)acetates through copper‐, silver‐, or phosphine‐catalyzed reaction of propiolates with 2′‐amino‐2,2,2‐trifluoroacetophenones. The approaches proposed ensure synthesis of substituted quinoline carboxylates and (indolin‐2‐ylidene)acetates in good yields. Introduction of alkynones into the reaction with 2′‐amino‐2,2,2‐trifluoroacetophenones gives acyl substituted derivatives in good yields. Based on Cu ang Ag catalysis as well as phosphine catalysis, we have developed efficient methods for the synthesis of three different types of CF3‐substituted compounds (quinoline‐3‐carboxylates, quinoline‐2‐carboxylates, and indolines) from the same starting materials such as o‐trifluoroacetylanilines and propiolates.