Radical Addition of Perfluoroalkyl Iodides to Alkenes and Alkynes Initiated by Sodium Dithionite in an Aqueous Solution in the Presence of a Novel Fluorosurfactant

Abstract

A new fluorinated anionic surfactant Cl(CF 2 ) 6 O(CF 2 ) 2 SO 3 N(C 2 H 5 ) 4 was prepared and characterized. The application of the fluorosurfactant allowed the fluoroalkylation to occur in the water without adding organic solvent. The addition of perfluoroalkyl iodides with olefins and alkynes under the initiation of Na 2 S 2 O 4 in water in the presence of the fluorosurfactant gave the corresponding adducts in good to excellent yields. The fluorosurfactant was suitable for a radical addition process.

Copper‐Catalyzed Trifluoromethylazidation of Alkynes: Efficient Access to CF3‐Substituted Azirines and Aziridines

“…In contrast, the catalytic trifluoromethylation of alkynes are still underdeveloped. Recently, the groups of Chen,11a Hu,11b and Cho11c reported the halotrifluoromethylation of alkynes. The groups of Szabó10e and Maiti11d reported the intermolecular oxytrifluoromethylation of alkynes, and in these reactions, addition of CF 3 radical to alkynes was proposed to provide a key CF 3 vinyl radical intermediate.…”

Perfluoroalkylation of alkenes and alkynes in water

“…10 Radical addition of perfluoroalkyl halides to carbon-carbon double bonds using transition metal catalysts has recently been reported. [11][12][13][14] Two effective radical perfluoroalkylations of some electron-deficient alkenes have been recently described: one affords the synthesis of chiral fluorinated aminoacids and peptides, and the other is based on the addition of perfluoroalkyl iodides to electron-deficient alkenes using aqueous 23 We have recently reviewed many non-carbon-centered radicals that are used in water to induce and accomplish several synthetically useful organic transformations. 24 Herewith, we describe a novel and easy methodology for the synthesis of perfluoroalkyl compounds, based on a radical reaction under thermal initiation by ACCN.…”

“…151(59), 133 (30), 102(100), 76(32), 75 (15), 74 (10), 69 (19), 53 (11). ESI-HRMS (negative mode, 60 eV) m/z: Calcd.…”

Frustrated-radical-pair-initiated atom transfer radical addition of perfluoroalkyl halides to alkenes

“…In contrast to the excellent examples achieved using metal-based catalyst systems (Scheme 1b), 12 organocatalysis has seldom been reported for such reactions. Moreover, current fluoroalkylation reactions initiated by catalytic amounts of the initiating agents typically require equivalent amounts of bases, 13 strong donor solvents 14 or flow reactors 15 (Scheme 1c). Recently, Vincent et al employed catalytic amounts of chloride ions to facilitate the homolytic cleavage of I–R F (R F = perfluoroalkyl) perfluoroalkyl iodides to accomplish the fluoroalkylation of alkenes (Scheme 1d).…”