Bidentate substrate binding in Brønsted acid catalysis: structural space, hydrogen bonding and dimerization
Johannes Gramüller, Philipp Dullinger, Dominik Horinek, Ruth M. Gschwind
Abstract
dimers. Molecular dynamics simulations showed that in these dimers, the imines form each one hydrogen bond to two CPA molecules, effectively bridging them. By finetuning steric repulsion and noncovalent interactions, rigid and well-defined CPA/imine monomers could be obtained. NOESY studies corroborated by theoretical calculations revealed the structure of that complex, in which the imine is located in between the 3,3'-substituents of the catalyst and one site of the substrate is shielded by the catalyst, pinpointing the origin or stereoselectivity for downstream transformations.
Topics & Concepts
CatalysisHydrogen bondDenticitySubstrate (aquarium)Brønsted–Lowry acid–base theoryChemistryHydrogenCombinatorial chemistryStereochemistryCrystallographyCrystal structureOrganic chemistryMoleculeBiologyEcologyAsymmetric Synthesis and CatalysisChemical Synthesis and AnalysisMolecular spectroscopy and chirality