Lewis Base Catalyzed Synthesis of Sulfur Heterocycles via the C1‐Pyridinium Enolate

While the addition of C1‐Lewis base enolates to carbonyls and related structures are well established, the related addition to thiocarbonyls compounds are unknown. Herein, we report a reaction cascade in which a C1‐pyridinium enolate undergos addition to dithioesters, trithiocarbonates and xanthates. The reaction provides access to a range of dihydrothiophenes and dihydrothiopyrans (28‐examples). Mechanistic investigations, including isolation of intermediates, electronic correlation, and kinetic isotope effect studies support the viability of an activated acid intermediate giving rise to the C1‐pyridinium enolate which undergoes turnover limiting cyclization. Subsequent formation of a β‐thiolactone regenerates the catalyst with loss of carbon oxysulfide providing the observed products.