Geminal Aminocyanation Enabled by Ylide Mediated Rearrangement.

Herein, we describe experimental and computational studies to understand the features of oxycyanopyridinium ylides generated in situ from oxy-cyanopyridines and rhodium carbene. This chemistry has enabled the concomitant formation of both C-N and C-C bonds, providing a complementary approach for cyanation reactions. Density functional theory calculations indicate the sequential metal-bound ylide formation, rhodium-associated five-membered transition state, and 1,4-cyano group relocation. Moreover, the enantioselective rearrangement has been realized by using chiral dirhodium complexes as the catalysts.