C-F Activation of Fluorinated Esters Using Photocatalytically Generated Diaminoalkyl Radical.

A method for hydrofluoroalkylation of alkenes with trifluoroacetic esters under visible light irradiation affording difluorinated products is described. The reaction involves readily available trimethyltriazinane as a shoichiometric reducing agent, which generates a diamino-substituted alkyl radical serving as a strong electron donor. It is believed that the cleavage of the C-F bond by a triazinane-derived radical involves single electron reduction coupled with fluoride transfer.

Dual Photoredox/Copper Catalyzed Fluoroalkylative Alkene Difunctionalization.

A method for performing radical difunctionalization of alkenes using fluorinated halides and a nucleophilic component (thiolate and iodide anions) is described. These nucleophilic fragments serve as redox active groups for performing subsequent transformations. The difunctionalization reaction involves photoredox generation of fluorinated radicals, their addition to the double bond followed by copper-promoted C-S or C-I bond formation. The primary products can be further coupled with silyl enol ethers, α-(trifluoromethyl)styrenes, and trimethylsilyl cyanide affording a variety of fluorinated compounds.

Aminals as powerful XAT-reagents: activation of fluorinated alkyl chlorides.

Readily available 1,3,5-trimethyl-1,3,5-triazinane serves as an efficient reagent for halogen atom transfer. Under photocatalytic conditions, the triazinane generates an α-aminoalkyl radical, which can activate the C-Cl bond of fluorinated alkyl chlorides. The hydrofluoroalkylation reaction between fluorinated alkyl chlorides and alkenes is described. The efficiency of the diamino-substituted radical derived from the triazinane is associated with stereoelectronic effects defined by a six-membered cycle forcing the anti-periplanar arrangement of the radical orbital and lone pairs of adjacent nitrogen atoms.

Organophotoredox-Catalyzed Reductive Tetrafluoroalkylation of Alkenes.

A method for the hydroperfluoroalkylation of alkenes with 1,2-dibromotetrafluoroethane leading to tetrafluorinated bromides is described. The reaction is conveniently performed under blue light irradiation using an organic photocatalyst and ascorbic acid as a reducing agent. Primary products can be further functionalized via radical pathways affording various tetrafluorinated compounds.

Atom-transfer radical addition of fluoroalkyl bromides to alkenes via a photoredox/copper catalytic system.

A method for the addition of fluorinated alkyl bromides to alkenes is described. The reaction proceeds under visible light irradiation in the presence of two catalysts: Ir(ppy)3 and N-heterocyclic carbene ligated copper bromide (IMesCuBr). The role of the iridium photocatalyst is to generate the fluoralkyl radical, while the copper promotes formation of the carbon-bromine bond.