A metal- and oxidant-free photoinduced strategy for thioxo sulfur-selective trifluoromethylation of β-ketodithioesters at room temperature is reported. Excellent /-stereoselectivity has been achieved with cheap and viable Langlois' reagent (CFSONa, sodium triflinate) in the presence of eosin Y, which acts as a hydrogen atom transfer (HAT) catalyst. The reaction proceeds disulfide intermediate disulfanediylbis(3-(alkylthio)-1-phenylprop-2-en-1-one) (a dimer of β-ketodithioester) followed by complementing proton-coupled electron transfer-mediated reverse HAT cycle of eosin Y. This operationally simple and efficient protocol allows direct access to triflinated α-oxoketene dithioacetals in good to excellent yields bearing diverse synthetically useful functional groups of different electronic and steric nature.
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