When Weaker Can Be Tougher: The Role of Oxidation State (I) in P- vs N-Ligand-Derived Ni-Catalyzed Trifluoromethylthiolation of Aryl Halides.

ABSTRACT: The direct introduction of the valuable SCF₃ moiety into organic molecules has received considerable attention. While it can be achieved successfully for aryl chlorides under catalysis with Ni⁰(cod)₂ and dppf, this report investigates the Ni-catalyzed functionalization of the seemingly more reactive aryl halides ArI and ArBr. Counterintuitively, the observed conversion triggered by dppf/Ni⁰ is ArCl > ArBr > ArI, at odds with bond strength preferences. By a combined computational and experimental approach, the origin of this was identified to be due to the formation of (dppf)Ni^I, which favors β-F elimination as a competing pathway over the productive cross-coupling, ultimately generating the inactive complex (dppf)Ni(SCF₂) as

SUBMITTER: Kalvet I 

PROVIDER: S-EPMC5339856 | biostudies-literature | 2017 Mar

REPOSITORIES: biostudies-literature