Palladium-Catalyzed Alkylation of Unactivated Olefins

Duke University, Durham NC

Investigators

Abstract

The foci of this research involve the palladium-catalyzed hydroalkylation and oxidative alkylation of unactivated olefins. The scope of hydroalkylation will be explored and the use of dialky ketones and electron-rich aryl groups will be used to develop processes for the formation of cyclopentanones, carbobicyclic and heterocyclic compounds. Intermolecular hydroalkylation processes will also be tested and the mechanism of palladium-catalyzed hydroalkylation wil be elucidated. Procedures for catalytic, asymmetric hdroalkylation will be developed as will tandem hydroalkylation/carbonylation and hydralkylation/carbometallation methodology. The scope of oxidative alkylation with respect to carbon nucleophiles and substitution will be examined and oxidative alkylation procedures terminated by beta-heteroatom elimination will be developed. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Ross A. Widenhoefer of the Department of Chemistry at Duke University. Professor Widenhoefer will focus his work on the development of methodologies for palladium-catalyzed alkylation of unactivated olefins. The chemistry holds great potential as a new method for C-C bond formation and could have an important broader impact on organic synthesis, in particular on the ability of synthetic chemists to construct complex naturally occurring and biologically active molecules of interest to the pharmaceutical industry. Aside from providing an excellent environment for the training of graduate students, the project will also involve participation of underrepresented minority undergraduate students from North Carolina Central University, a neighboring HBCU.