Journal of the American Chemical Society · 2014 · 62 citations · 67 references
Natural SciencesChemistryBiocatalysisCatalysisEnzyme MechanismCatalytic MechanismsCross-coupling ReactionsEnzymatic CatalysisEnzyme KineticsLigand BindingLigand-based DesignAldehydesAtom Economy In Coupling ReactionsCatalytic Reaction MechanismsEnantioselective Cross-couplingLigand DesignLigand Design For Cross-couplingMechanistic Studies Of Cross-couplingStereochemical Mechanisms
Under Rh(I) catalysis, α-ketoamides undergo intermolecular hydroacylation with aliphatic aldehydes. A newly designed Josiphos ligand enables access to α-acyloxyamides with high atom-economy and enantioselectivity. On the basis of mechanistic and kinetic studies, we propose a pathway in which rhodium plays a dual role in activating the aldehyde for cross-coupling. A stereochemical model is provided to rationalize the sense of enantioinduction observed.
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