An efficient method for the reductive transposition of allylic alcohols

Article abstract of DOI:10.1016/0040-4039(96)00965-3

The Mitsunobu reaction of allylic alcohols with o- nitrobenzenesulfonylhydrazine (NBSH) as nucleophile proceeds at -30 °C with invertive displacement; warming the resultant N-allylic sulfonylhydrazine derivative to 23 °C then leads to allylic diazene formation followed by sigmatropic elimination of dinitrogen. This one-step method for reductive 1,3-transposition is shown to be efficient and highly regio- and stereocontrolled within a wide range of allylic alcohol substrates.