Mechanistic and computational studies of oxidatively-induced aryl-CF3 bond formation at palladium

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Abstract

This article describes the rational design of 1st generation systems for oxidatively-induced Aryl– CF3 bond-forming reductive elimination from PdII. Treatment of (dtbpy)PdII(Aryl)(CF3) (dtbpy = di-tert-butylbipyridine) with NFTPT (N-fluoro-1,3,5-trimethylpyridium triflate) afforded the isolable PdIV intermediate (dtbpy)PdIV(Aryl)(CF3)(F)(OTf). Thermolysis of this complex at 80 °C resulted in Aryl–CF3 bond-formation. Detailed experimental and computational mechanistic studies have been conducted to gain insights into the key reductive elimination step. Reductive elimination from this PdIV species proceeds via pre-equilibrium dissociation of TfO− followed by Aryl–CF3 coupling. DFT calculations reveal that the transition state for Aryl–CF3 bond formation involves the CF3 acting as an electrophile with the Aryl ligand acting as a nucleophilic coupling partner. These mechanistic considerations along with DFT calculations have facilitated the design of a 2nd generation system utilizing the tmeda (N,N,N’,N’-tetramethylethylenediamine) ligand in place of dtbpy. The tmeda complexes undergo oxidative trifluoromethylation at room temperature.

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JournalFaculty Publications
DOIs
StatePublished - Jan 1 2010

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