Furfuryl Cation Induced Three‐Component Reaction to Synthesize Triazole‐Substituted Thioesters

A furfuryl cation induced three‐component thioesterification reaction between thiols, 5‐bromo‐2‐furylcarbinols and azides is reported. This metal‐free method relies on the acetyl chloride/HFIP‐mediated cascade formal [3+2] cycloaddition/ring‐opening/thioesterification, which allows the efficient construction of a series of complex triazole‐thioesters linked with an (Z)‐olefin. Selenols are also suitable for this strategy. Further derivatization of thioesters highlighted the potential utility of our method. A metal‐free three‐component thioesterification between thiols, 5‐bromo‐2‐furylcarbinols, and azides that provides rapid access to thioesters bearing a triazole moiety, highlighted by the cascade [3+2] cycloaddition/furan ring‐opening/thioesterification, is disclosed. Selenols are also suitable for this reaction. The new reaction features simple reaction conditions of AcCl/HFIP and a general substrate scope.