Organocatalytic Sigmatropic Reactions: Development of a [2,3] Wittig Rearrangement through Secondary Amine Catalysis

Simple secondary amine organocatalysts induce a general [2,3] Wittig rearrangement via an enamine under extremely mild conditions. The organocatalytic rearrangement gives good diastereoselectivities over a range of substrates and generates the syn isomer, which is contrary to what would be expected from the conventional [2,3]-reaction.