Synthesis and Reactivity of Fluoroalkyl Copper Complexes by the Oxycupration of Tetrafluoroethylene

Abstract

The copper(I)-mediated generation of -OCF CF - moieties by the oxycupration of tetrafluoroethylene (TFE) using either copper aryloxides or alkoxides is disclosed. The key intermediates, 2-aryloxy-1,1,2,2-tetrafluoroethyl and 2-alkoxy-1,1,2,2-tetrafluoroethyl copper complexes, were obtained from the reaction of the corresponding aryloxy and alkoxy copper complexes with TFE, and their structures in solution and in the solid state were unambiguously determined by multinuclear NMR spectroscopy and X-ray diffraction analysis. These copper complexes subsequently reacted with aryl iodides (ArI) to afford ROCF CF Ar (R=aryl or alkyl) in high yields.

Controllable double CF2-insertion into sp2 C–Cu bond using TMSCF3: a facile access to tetrafluoroethylene-bridged structures

“…Current methods for the syntheses of tetrauoroethylenebridged structures are mainly based on (1) deoxouorination of 1,2-dicarbonyl compounds with SF 4 and DeoxoFluor; [9][10][11] (2) uorination of C-C triple bonds using F 2 ; [12][13][14] (3) 1,2-difunctionalization of tetrauoroethylene (TFE); [15][16][17][18][19][20][21][22][23] (4) diuoromethylene insertion using CF 2 Br 2 as the CF 2 source; 24,25 and (5) using RCF 2 CF 2 Br as the build block. 5 However, these methods suffer from several drawbacks such as (1) using toxic, highly reactive or hazardous reagents; (2) low functional group tolerance and/or (3) using explosive gaseous reagents or ozonedepleting substances (ODS).…”

Advances in the Synthesis and Application of Tetrafluoroethylene‐ and 1,1,2,2‐Tetrafluoroethyl‐Containing Compounds

“…Carbocupration of TFE provides 2‐aryl‐1,1,2,2‐tetrafluoroethylcopper species 33 (Scheme ), which are unstable in the presence of Lewis acids . Similarly, oxycupration of TFE by copper phenoxide and alkoxide complexes provides 2‐aryloxy and 2‐alkoxy‐1,1,2,2‐tetrafluoroethylcopper compounds 34 (Scheme ) . The reactivity of 33a , 34a – c and other in situ‐formed 2‐aryl‐ and 2‐aryloxy‐1,1,2,2‐tetrafluoroethylcopper compounds is described in Chapter 3.3.…”

“…The in situ‐formed Cu I reagents were also later used for the synthesis of trifluorostyrene derivatives via β‐fluorine elimination promoted by the addition of NaI as a Lewis acid . Very recently, they reported analogous procedure for oxycupration of tetrafluoroethylene, thus forming the corresponding organocopper reagents 34 useful in the synthesis of various tetrafluoroethyl alkyl or aryl ethers (Scheme ) . By changing the solvent to DMF, the authors even managed to perform the one‐pot synthesis without the need of the phenanthroline ligand.…”

Nickel‐Catalyzed Reductive Coupling for Transforming Unactivated Aryl Electrophiles into β‐Fluoroethylarenes

“…[1] Numerous practices of drug modification demonstrated that the precisely-controlled introductiono ff luorine atoms could be highly beneficial for improving the pharmacological properties of candidate compounds such as lipophilicity,m etabolic stabilitya nd binding affinity. [4] These methods are highlighted by the mildness of reactionc onditions and the synthetic convergences from widely available fluorine-containing buildingb locks such as fluoroolefin [5] and fluoroalkyl halides. [4] These methods are highlighted by the mildness of reactionc onditions and the synthetic convergences from widely available fluorine-containing buildingb locks such as fluoroolefin [5] and fluoroalkyl halides.…”