Ether-directed palladium(II)-catalysed aza-Claisen rearrangements: studies on the origin of the directing effect

Four new chiral δ-substituted allylic trichloroacetimidates have been synthesised to probe the origin of the high diastereoselectivity observed for the MOM-ether directed palladium(II)-catalysed aza-Claisen rearrangement. Rearrangement of these compounds has not only provided strong evidence for this directing effect but also that during the rearrangement both oxygen atoms from the MOM-ether are involved in coordinating to and directing the palladium(II) catalyst.