Palladium-catalyzed rearrangement and substitution reactions of acyclic vinylogous carbonates and sulfonates: Development of a new leaving group for Pd-allyl chemistry

Article abstract of DOI:10.1016/S0040-4039(99)00475-X

Palladium-catalyzed rearrangement of the deuterium labeled vinylogous carbonate 1 furnished the β-formyl esters 3a/b in 68% yield, while the Z- vinylogous sulfonate (Z-VINS) 2 under analogous reaction conditions led to reversible O-alkylation and isomerization to afford the E-VINS 4a/b in 61% yield. This observation prompted the development of the vinylogous sulfonate as an improved leaving group for a variety of palladium-catalyzed allyIic substitution reactions.