Chiral amines are ubiquitous motifs in organic molecules of societal value. The synthesis of certain chiral amines remains a synthetic challenge. Presented herein is an unusual approach to chiral amine synthesis that utilizes the spontaneous rearrangement of allylic azides (Winstein Rearrangement). One component of the equilibrating mixture can be selectively trapped, establishing the amine bearing stereocenter. However, accomplishing this in practice requires high levels of selectivity and the simultaneous application of numerous control elements. Approaches to enabling selectivity will be described along with synthetic applications of the reactions, including in the synthesis of heterocyclic products.
Joseph Topczewski (University of Minnesota)