Nickel‐Catalyzed Three‐Component Coupling Reaction of Tetrafluoroethylene and Aldehydes with Silanes via Oxa‐Nickelacycles

Abstract

The nickel‐catalyzed synthesis of a variety of fluorine‐containing silyl ethers from tetrafluoroethylene (TFE) and aldehydes with silanes in a selective manner is disclosed. Stoichiometric reactions revealed that the oxa‐nickelacycle, which is generated upon oxidative cyclization of TFE and an aldehyde with Ni0, is the key intermediate, whose molecular structure was confirmed by single‐crystal X‐ray diffraction analysis. In order to demonstrate the synthetic utility of this procedure, one of the reaction products was transformed into trifluorovinyl and organic silicon compounds via deprotonation with a Lewis base.

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).…”

Ni-catalyzed hydroalkylation of olefins with N-sulfonyl amines

“…In 2020, Koh's group developed an aminoquinaldine-directed hydroalkylation reaction, in which one alkyl halide molecule provides an alkyl motif and another delivers a hydride via β-H elimination 46 . In addition to alkyl halides, imines or aldehyde can also be used as coupling partners for hydroalkylation reactions of tetrafluoroethylene with silanes 47,48 .…”

Linking Mechanistic Analysis of Catalytic Reactivity Cliffs to Ligand Classification

“…Interestingly, even in the data for Ni-catalyzed cross-couplings, the most active ligands generally fell within these limits (Figure 2). This observation suggests that L1 intermediates and/or transition states may be relevant in Ni catalysis (50,51), but that the ability to attain an L2 resting state is necessary (33,52,53), as evidenced by the sharp reactivity cliffs.…”