Substrate-Controlled Product Divergence: Silver-Catalyzed Reaction of Trifluoromethyl Ketones with Terminal Alkynes

A distinct dichotomy in product distribution was initially observed in the silver-catalyzed reaction of trifluoromethyl (CF3) ketones with terminal alkynes having two different types of electronic natures. The domino reaction smoothly proceeded almost exclusively with high stereoselectivity with terminal alkynes containing ester groups, whereas alkynylation occurred in good yield when terminal alkynes containing aryl or alkyl groups were present. The results indicated that the electronic nature of terminal alkynes can act as a switch that enables either the domino reaction or alkynylation between terminal alkynes and CF3 ketones.