Metal-Free C-C Coupling of an Allenyl Sulfone with Picolyl Amides to Access Vinyl Sulfones via Pyridine-Initiated In Situ Generation of Sulfinate Anion.

Vinyl sulfones are privileged motifs known for their biological activity and synthetic utility. Synthetic transformations to efficiently access high-value compounds with these motifs are desired and sought after. Herein, a new procedure is described to form vinyl sulfone-containing compounds by selective functionalization of the C(sp3)-H bond adjacent to the pyridine ring of pharmacologically prevalent picolyl amides with an allenyl sulfone, 1-methyl-4-(propa-1,2-dien-1-ylsulfonyl)benzene. The reaction conditions are mild with no metal catalyst or additives required and display good functional group tolerance. Mechanistic studies for this unusual transformation suggest that the reaction operates via a rare pyridine-initiated and p-toluenesulfinate anion-mediated activation of the allenyl sulfone analogous to phosphine-triggered reactions.