Difluoro-lambda3-bromane-induced oxidative carbon-carbon bond-forming reactions: ethanol as an electrophilic partner and alkynes as nucleophiles

Abstract

Reported here for the first time are the oxidative couplings of alkynes and primary alcohols yielding conjugated enones. Although the BF3-catalyzed reaction of terminal alkynes with p-trifluoromethylphenyl(difluoro)-lambda3-bromane results in the fluoro-lambda3-bromanation of triple bonds to afford (E)-beta-fluorovinyl-lambda3-bromanes, reaction of an alkyne with the difluoro-lambda3-bromane in the presence of an alcohol and BF3-Et2O affords directly conjugated enones in good yields. The reaction proceeds in a highly stereo- and regioselective manner under metal-free conditions. Interestingly, no formation of enones was detected, when difluoro-lambda3-iodane p-CF3C6H4IF2 was used instead of the lambda3-bromane. A mechanism involving a lambda3-bromane-induced oxidation of an alcohol to an aldehyde, [2 + 2] cyclization with alkynes yielding 2H-oxetes, and finally the electrocyclic ring opening is discussed.