A General One-Step Method for the Conversion of Alcohols with Weak Nitrogenous Nucleophiles

Significance

The authors report a general room-temperature procedure for the direct, regioselective substitution of the hydroxy group in allylic, propargylic and benzylic alcohols with sulfon­amides, carbamates and carboxamides, all of which are known to be relatively weak nucleophiles. A commercially available Bi(OTf)₃/KPF₆ catalytic system is used delivering the respective amides in moderate to excellent yields under mild reaction conditions. The definitive advantage of this method is the excellent generality, including the conversion of cyclic and acyclic, benzylic and non-benzylic allylic and even of tertiary propargylic alcohols and its regioselectivity - allylic alcohols have been found to be attacked in the sterically less hindered position, whereas in propargylic alcohols the nucleophile occupies the original position of the hydroxyl group.