Superelectrophilic Fe(III)–Ion Pairs as Stronger Lewis Acid Catalysts for (<i>E</i>)-Selective Intermolecular Carbonyl–Olefin Metathesis
Haley Albright, Hannah L. Vonesh, Corinna S. Schindler
Abstract
An intermolecular carbonyl–olefin metathesis reaction is described that relies on superelectrophilic Fe(III)-based ion pairs as stronger Lewis acid catalysts. This new catalytic system enables selective access to (E)-olefins as carbonyl–olefin metathesis products. Mechanistic investigations suggest the regioselective formation and stereospecific fragmentation of intermediate oxetanes to be the origin of this selectivity. The optimized conditions are general for a variety of aryl aldehydes and trisubstituted olefins and are demonstrated for 28 examples in up to 64% overall yield.
Topics & Concepts
ChemistryCatalysisIntermolecular forceOlefin metathesisOlefin fiberMetathesisLewis acids and basesIonMedicinal chemistrySalt metathesis reactionOrganic chemistryMoleculePolymerizationPolymerSynthetic Organic Chemistry MethodsOrganic and Inorganic Chemical ReactionsOrganoboron and organosilicon chemistry