A General, Regiospecific Synthetic Route to Perfluoroalkylated Arenes via Arenediazonium Salts with R_FCu(CH₃CN) Complexes

Abstract

A mild method of converting arylamines into perfluoroalkylated arenes is described. Relatively stable RFCu(CH3CN) complexes are used as perfluoroalkylating agents, which react smoothly with arenediazonium salts to produce various perfluoroalkylarenes in good yields. Based on the results of clock trapping experiments with diallyl ether, a radical process might be involved in the reaction.

Syntheses, structures, and stabilities of aliphatic and aromatic fluorous iodine(I) and iodine(III) compounds: the role of iodine Lewis basicity

“…An analogous procedure with R f10 I gave the higher homolog 1,3-R f10 C 6 H 4 I in 50% yield [ 9 ], and a lesser amount of what was presumed to be the dialkylation product. The analogous para diiodide 1,4-C 6 H 4 I 2 gave parallel chemistry, as illustrated by the reaction with R f6 I to give 1,4-R f6 C 6 H 4 I (50% [ 4 , 12 ]) in Scheme 5 (bottom).…”

“…Fluorous aryl iodides, such as R f n C 6 H 4 I or R f n (CH 2 ) m C 6 H 4 I species, are also often employed as intermediates (typically m = 2, 3 and n ≥ 6 [ 1 – 3 ]), but only a few have been commercialized [ 4 ]. Many research groups have described the syntheses of other types of fluorous alkyl [ 5 – 8 ] and aryl [ 9 – 12 ] iodides [ 13 – 17 ]. The former are ubiquitous by virtue of the large number of perfluoroalkyl iodides R f n I that have been shown to undergo free radical additions to alkenes [ 7 – 8 ].…”

Acetamidoarenediazonium Salts: Opportunities for Multiple Arene Functionali­zation

“…To the best of our knowledge, Pd‐catalyzed coupling reactions have not previously been investigated for arenediazonium salts substituted with acetamide groups. However, diazonium salts m ‐ and p ‐ 2a have been used in the Balz–Schiemann reaction,32 inter alia for the synthesis of radiolabelled fluoroarenes,33 in Cu‐catalyzed difluoromethylations34 and perfluoroalkylations,41 and for the site‐selective modification of genetically engineered proteins through azo coupling 42…”

Copper-Promoted Trifluoromethanesulfonylation and Trifluoromethylation of Arenediazonium Tetrafluoroborates with NaSO2CF3

“…After purification by silica gel column chromatography using n-hexane/ethyl acetate (5/1) as the eluent, compound 2q was obtained as a white solid (24. 9,147.5,142.0,134.8,130.0,129.7,129.2,126.1,124.5,119.7 (q,. 19 General procedure for trifluoromethylation of arenediazonium tetrafluoroborate with NaSO 2 CF 3 .…”