In this context, we reported a visible-light-mediated [2 + 2 + 1] cascade cyclization of 1,6-enynes with thiols, providing a new synthetic protocol for the rapid construction of sulfur-containing polycyclic derivatives in moderate to good yields along with a broad substrate scope. Mechanistic investigations were also performed by control experiments and Stern-Volmer analysis as well as DFT calculations, suggesting that this cascade cyclization reaction stems from a sulfur radical addition to the alkynyl moiety of 1,6-enyne along with a cascade cyclization with the alkenyl unit. Then, the formation of sulfur-containing polycyclic can be achieved by homolytic SHi-type substitution at the thioether unit to stripping the sulfur atom. The further transformations of the obtained product have been also disclosed.

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