Ferrier Rearrangement under Nonacidic Conditions Based on Iodonium-Induced Rearrangements of Allylic n-Pentenyl Esters, n-Pentenyl Glycosides, and Phenyl Thioglycosides

Article abstract of DOI:10.1021/jo00117a042

Iodonium-promoted rearrangements of easily accessible allylic n-pentenyl esters, n-pentenyl glycosides, or phenyl thioglycosides result in the generation of the allylic oxocarbenium ion intermediate II of the Ferrier rearrangement, I -> II -> IIIa, of glycals leading to 2,3-unsaturated glycosides.Thus the Ferrier rearranmgement can now be carried out under nonacidic conditions, with NIS or iodonium dicollidinium perchlorate as promoter, to afford good yields of disaccharides in which acid-labile functionalities, either in the glycosyl donor or glycosyl acceptor, have been preserved.