On the palladium(II)-catalyzed rearrangement of allyl imidates

Article abstract of DOI:10.1016/S0040-4020(01)88203-X

Polyhetero-[3,3]-sigmatropic rearrangements of allyl N-phenylimidates 4a-f catalyzed by dichlorobis-(benzonitrile)palladium(II) are shown to afford N-allyl-N-phenylamides in good to excellent yields for substitution patterns that have so far precluded cyclization-induced allyl shifts. Using trichloroacetimidates of secondary allyl alcohols as substrates, the palladium(II)-catalyst effects a completely (E) stereoselective rearrangement at room temperature which proceeds with complete chirality transfer. This reaction has been applied to a synthesis of (R)-N-(trichloroacetyl)norleucinol (18) starting from (R)-2,3-O-isopropylideneglyceraldehyde (17).