1. Introduction.

Enantioenriched allylic amines are versatile synthetic intermediates and constituents of biologically active molecules of therapeutic interest, but traditional asymmetric approaches to amines are incompatible.                                        

2. Results.  

We have developed an organocatalytic a-sulfenation/olefination reaction transforming aldehydes into allylic sulfides. An oxaziridine 3 then effects amination/[2,3]-sigmatropic rearrangement, which followed by in situ N-S bond cleavage provides access to allylic amines (Scheme 1).

This demonstrates the first asymmetric synthesis of a variety of allylic sulfides, and the first example of complete chirality transfer, asymmetric synthesis of vinyl glycine derivatives and quaternary stereocentres during sulfimide rearrangement. Additional versatility resulted from rearrangement of the alternative alkene isomer to provide the opposite stereoisomer of the amine, removing the need to employ a more expensive un-natural catalyst.  

3. Conclusion.  

We have developed a two-step non-metallic approach to a variety of highly challenging enantioenriched vinyl glycine motifs which were previously unobtainable through existing methodology (Scheme 2).