The Role of Ate Complexes in the Copper-Mediated Trifluoromethylation of Alkynes.

Abstract

Trifluoromethylation reactions have recently received increased attention because of the beneficial effect of the trifluoromethyl group on the pharmacological properties of numerous substances. A common method to introduce the trifluoromethyl group employs the Ruppert-Prakash reagent, that is, Si(CH3 )3 CF3 , together with a copper(I) halide. We have applied this method to the trifluoromethylation of aromatic alkynes and used electrospray-ionization mass spectrometry to investigate the mechanism of these reactions in tetrahydrofuran, dichloromethane, and acetonitrile as well as with and without added 1,10-phenanthroline. In the absence of the alkyne component, the homoleptic ate complexes [Cu(CF3 )2 ](-) and [Cu(CF3 )4 ](-) were observed. In the presence of the alkynes RH, the heteroleptic complexes [Cu(CF3 )3 R](-) were detected as well. Upon gas-phase fragmentation, these key intermediates released the cross-coupling products R-CF3 with perfect selectivity. Apparently, the [Cu(CF3 )3 R](-) complexes did not originate from homoleptic cuprate anions, but from unobservable neutral precursors. The present results moreover point to the involvement of oxygen as the oxidizing agent.