Chemo-, regio-, and stereoselective tetrafunctionalization of fluoroalkynes enables divergent synthesis of 5-7-membered azacycles.

Alkyne annulation has been widely used in organic synthesis for the construction of azacycles with unique structural and physicochemical properties. However, the analogous transformation of fluoroalkynes remains a challenge and has seen limited progress. Herein we report a 1,2,3,4-tetrafunctionalization of polyfluoroalkynes for the divergent construction of 5-7-membered ()-1,2-difluorovinyl azacycles.

Synthesis of di(hetero)aryl sulfides by defluorinative sulfenylation of polyfluoroalkyl ketones with sodium sulfinates or arylsulfonyl chlorides.

A facile incorporation of a privileged sulfide, a naphthofuran framework, and a perfluoroalkyl moiety in one molecule was successfully accomplished through tandem defluorinative sulfenylation of α-perfluoroalkyl ketones with a sulfur source. The reaction presumably proceeds via a sequence involving defluorination, reductive sulfenylation, autoaromatization, and annulation, accompanied by the simultaneous cleavage of four C(sp)-F bonds and the formation of new C-S and C-O bonds.