Phosphorylation Organocatalysts Highly Active by Design
Amit Fallek, Mor Weiss-Shtofman, M. S. Kramer, Roman Dobrovetsky, Moshe Portnoy
Abstract
The activity of nucleophilic organocatalysts for alcohol/phenol phosphorylation was enhanced through attaching oligoether appendages to a benzyl substituent on imidazole- or aminopyridine-based active units, presumably because of stabilizing n–cation interactions of the ethereal oxygens with the positively charged aza-heterocycle in the catalytic intermediates, and was substantially higher than that of known benchmark catalysts for a range of substrates. Density functional theory calculations and the study of analogues having a lower potential for such stabilizing interactions support our hypothesis.
Topics & Concepts
ChemistrySubstituentNucleophileImidazoleCatalysisPhosphorylationCombinatorial chemistryDensity functional theoryStereochemistryOrganic chemistryComputational chemistryBiochemistryChemical Synthesis and AnalysisAsymmetric Synthesis and CatalysisOrganophosphorus compounds synthesis