Synthesis of chiral 3E,5E-octadiene-1,2R-7R,8-tetraol frameworks by means of palladium(II)-promoted hetero-Claisen rearrangement: Mechanistic aspect

Article abstract of DOI:10.1016/0040-4020(96)00854-X

A plausible mechanism has been proposed for the exclusive formation of symmetrical dienediol such as 1,6-bis(acetoxy)-2,4-diene in palladium(II)-promoted [3,3]sigmatropic rearrangement of 3,4-bis(acetoxy)-1,5-diene system. This mechanism referred to as migration-induced intramolecular dioxanium ion switching (MIDIS) process can reasonably explain why the vicinal acetoxy groups move from 3,4-position and not to 5,6- but two directionally to 1,6-position.