Deprotonation of benzylic ureas, carbamates, and thiocarbamates bearing N′-alkenyl substituents generates carbanions which undergo intramolecular migration of the alkenyl group to the carbanionic center. Solvolysis of the urea products generates α-alkenylated amines. With an enantiomerically pure starting urea, migration proceeds stereospecifically, generating in enantiomerically enriched form products containing allylic quaternary stereogenic centers bearing N. Computational and in situ IR studies suggest that the reaction, formally a nucleophilic substitution at an sp 2 carbon atom, proceeds by a concerted addition-elimination pathway.
|Number of pages||4|
|Journal||Journal of the American Chemical Society|
|Early online date||15 Apr 2012|
|Publication status||Published - 2 May 2012|