Photocatalytic perfluoroalkylation of disulfides and diselenides. Syntheses of perfluoroalkyl thio- and seleno-ethers

The synthesis of alkyl(aryl)-fluoroalkyl sulfanyl [R(Ar)-S-R-F] and aryl-fluoroalkyl selenolyl (Ar-Se-R-F) ethers through visible-light photocatalysis has been successfully carried out. This process involves disulfides, and diselenides [R(Ar)-X-X-R(Ar), where X = S or Se], and fluoroalkyl iodides (R-F-I) in the presence of a base as an additive under photocatalysis. The photocatalyst Eosin Y and green light-emitting diodes are utilized for irradiation of R(Ar)-S-R-F and Ar-Se-R-F syntheses. Our method integrates low-energy visible-light photocatalysis, commercially available perfluoroalkylating reagents (R-F-I), and easily obtainable disulfides and diselenides as starting materials. Mechanistic studies and a detailed synthetic procedure for (Ar)-S-R-F on a large scale are presented.