In the Lautens research group, palladium-catalyzed intramolecular carbohalogenation reactions have been recently developed. In addition to the useful and novel halogenated compounds produced by these protocols, these transition metal-catalyzed processes are also highly atom economical in nature. Through simple computational analysis we were able to identify substrates that could potentially exhibit high levels of chirality transfer. Optimization studies were then undertaken to discover experimental conditions that allowed for the formation of neopentyl iodide-containing heterocycles in high yields and excellent diastereoselectivities. The correlation of theory and experiment is quite remarkable due to the low-level computational basis set used, requiring extremely short periods of CPU usage. We are actively exploring and expanding the substrate scope of this Pd-catalyzed diastereoselective carbohalogenation reaction for the synthesis of chiral chromans. We are also continuing to utilize computational predictions in tailoring our approach to nitrogen-containing heterocycles as the project progresses.

Theoretical basis for diastereoselectivity in palladium-catalyzed carbohalogenation reactions

244th National Meeting (2012)

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