Catalytic asymmetric halocyclizations, powered by chlorinated hydantoins and the dimeric cinchona alkaloid catalyst, (DHQD)2PHAL, has demonstrated utility as a robust transformation to access halogenated products in high enantiomeric excess. With the increase of reported asymmetric halocyclization reactions, the need for a better mechanistic understanding of these transformations is necessary for rational optimization of both reaction yields and enantioselectivity. Additionally, it allows for the further expansion into a new family of reactants. Absolute and relative stereochemistry, formed by addition across the double bond for unsaturated amides and carbamates is reported utilizing deuterium isotope labeling, spectroscopic analysis, and analog studies. To guide further clarification of these classes of transformations, mechanistic studies and kinetic analyses will be presented.                                             

Mechanistic investigations of the asymmetric organocatalytic chlorocyclization reaction

245th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.