Catalytic Cycle for Palladium-Catalyzed Decarbonylative

Organometallics , 2014, 33 (10), pp 2653–2660. DOI: 10.1021/om500398z. Publication Date (Web): May 12, 2014. Copyright © 2014 American Chemical ...
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Catalytic Cycle for Palladium-Catalyzed Decarbonylative Trifluoromethylation using Trifluoroacetic Esters as the CF3 Source Ansis Maleckis and Melanie S. Sanford* Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor Michigan 48109, United States S Supporting Information *

ABSTRACT: This paper demonstrates a catalytic cycle for Pd-catalyzed decarbonylative trifluoromethylation using trifluoroacetic esters as CF3 sources. The proposed cycle consists of four elementary steps: (1) oxidative addition of a trifluoroacetic ester to Pd0, (2) CO deinsertion from the resulting trifluoroacyl PdII complex, (3) transmetalation of a zinc aryl to PdII, and (4) aryl−CF3 bond-forming reductive elimination. The use of RuPhos as the supporting ligand enables each of these steps to proceed under mild conditions (