Journal of the American Chemical Society · 2009 · 318 citations · 26 references
Natural SciencesChemistryCatalysisOrganic ChemistryOrganometallic ChemistryCross-coupling ReactionsOrganic SynthesisReductive EliminationCatalytic Cycle AnalysisCatalytic Cycle MechanismsFluorination ProcessesFluorine ChemistryPalladium CatalystsReductive Elimination From Palladium ComplexesReductive Elimination MechanismRegioselectivity
A novel palladium-catalyzed intramolecular oxidative aminofluorination of unactivated alkenes has been developed, in which AgF was used as a key fluorinating reagent and PhI(OPiv)(2) as oxidant. The reaction afforded vicinal fluoroamine products with very high regioselectivity. A Pd(II/IV) catalytic cycle was proposed, and preliminary mechanistic studies indicated that direct reductive elimination of Pd(IV) intermediates is favored, albeit competing with S(N)2 nucleophilic attack by fluorine, to form a C-F bond.
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