A Catalyst-Controlled Enantiodivergent Bromolactonization
Yuk‐Cheung Chan, Xinyan Wang, Ying‐Pong Lam, Jonathan Wong, Ying‐Lung Steve Tse, Ying‐Yeung Yeung
Abstract
A catalyst-controlled enantiodivergent bromolactonization of olefinic acids has been developed. Quinine-derived amino-amides bearing the same chiral core but different achiral aryl substituents were used as the catalysts. Switching the methoxy substituent in the aryl amide system from meta- to ortho-position results in a complete switch in asymmetric induction to afford the desired lactone in good enantioselectivity and yield. Mechanistic studies, including chemical experiments and density functional theory calculations, reveal that the differences in steric and electronic effects of the catalyst substituent alter the reaction mechanism.
Topics & Concepts
ChemistrySubstituentSteric effectsAmideCatalysisArylAsymmetric inductionYield (engineering)Density functional theoryStereochemistryEnantioselective synthesisElectronic effectComputational chemistryOrganic chemistryMaterials scienceAlkylMetallurgyVanadium and Halogenation ChemistryOxidative Organic Chemistry ReactionsAsymmetric Synthesis and Catalysis