Electron-catalyzed radical perfluoroalkylation of organic sulfides: the serendipitous use of the TMEDA/I₂ complex as a radical initiator

Abstract

The (TMEDA)I·I3 complex as a new radical initiator for the perfluoroalkylation of RSH.

Radical fluoroalkylation reactions of (hetero)arenes and sulfides under red light photocatalysis

“…450-550 nm). Through visible light-induced (white light) organic-dye photocatalysis, our group has studied the perfluoroalkykation reactions of aromatic amines, 8 thiols, 9 and heteroaromatic-N-oxides. 10 Polypyridyl metal complexes such as Ir( ppy) 3 and Ru(bpy) 3 are key catalysts in this event, and blue-or white-light irradiation (λ = 375-450 nm) is required for the chemical transformations.…”

“…Radical photocatalytic perfluoroalkylation of sulfides has been pursued with Ru(bpy) 3 Cl 2 as photocatalyst 22 under white light irradiation (CFL), or through visible-light-photoexcited EDA complexes, 9 among the most recent environmentallybenign radical-based strategies.…”

Synthetic Studies on the Incorporation of N-Acetylallosamine in Hyaluronic Acid-Inspired Thiodisaccharides

“…Using a classic S N 2 approach, in a 2-step reaction ( Scheme 1 ), we first treated 1 with Tf 2 O/py to obtain the 3- O -triflate derivative 2 which was not isolated from the reaction medium [ 10 , 30 ]. The addition of the GlcA-derived thioaldose 3 [ 9 , 31 , 32 ] and NEt 3 in anhydrous DMF at 0 °C, led to thiodisaccharide 4 , which could be successfully recovered from the reaction mixture and purified by column chromatography.…”

Radical Fluoroalkylation Reactions

“…Chen and colleagues 75 The perfluoroalkylation of sulfides has also been reported to proceed in the absence of photocatalysts and presence of organic base TMEDA. 7…”