Visible-Light-Induced Atom Transfer Radical Addition and Cyclization of Perfluoroalkyl Halides with 1,n-Enynes

A mild and efficient visible-light-induced atom transfer radical addition and cyclization of 1,n-enynes (n = 6, 7) with perfluoroalkyl halides, leading to halo-perfluorinated N-heterocycles, has been developed. This protocol offers a mild, completely atom-economic, and general access to perfluorinated 2,4-dihydronquinolin-2(1H)-ones and pyrrolidines from corresponding benzene and N-tethered 1,n-enynes (n = 6, 7) via 5,-6-exo-dig cyclization, allowing for the expedient incorporation of a wide variety of perfluorinated groups, such as CF3, i/n-C3F7, n-C4F9, n-C6F13, n-C6F17, nC(8)F(17), n-C10F21, CF2Br, CF2CO2Et, etc. In addition, the reactions using 1,7-enynes (n = 6, 7) bearing a tert-butyl-linked alkynyl moiety enable a divergent cyclization involving a hydrogen atom transfer (HAT) process, thereby leading to novel alpha,alpha-haloperfluorinated 2,4-dihydronquinolin-2(1H)-ones.