Controllable Single and Double Difluoromethylene Insertions into C-Cu Bonds: Copper-Mediated Tetrafluoroethylation and Hexafluoropropylation of Aryl Iodides with TMSCF2H and TMSCF2Br.

Abstract

The selective difluoromethylene insertion into a C-Cu bond is a challenging task and is currently limited to either a single CF2 insertion into CuCF3 or double CF2 insertions into CuC6F5 (or (Z)-CF3CF = CFCu). Achieving both selective single and double CF2 insertions into the same C-Cu bond is even more difficult. Herein, highly controllable single and double CF2 insertions into CuCF2H species with a TMSCF2Br reagent have been described, affording two previously unknown fluoroalkylcopper species "Cu(CF2)nCF2H" (n = 1 and 2) independently under different reaction conditions. This work represents the first example of both single and double CF2 insertions into the same C-Cu bond in a highly selective manner. The synthetic value of the obtained "Cu(CF2)nCF2H" (n = 1 and 2) species is demonstrated by their reactions with aryl iodides, halogenation agents, and cinnamyl chloride, which enables the direct transfer of HCF2CF2 and HCF2CF2CF2 moieties into organic molecules. The key to controllable fluorocarbon chain elongation from C1 to C2 and from C1 to C3 is presumably attributed to the different reactivities of "Cu(CF2)nCF2H" species (n = 0, 1, 2 and 3) and the loading of the TMSCF2Br reagent.