Christopher J. Douglas, University of Minnesota - Twin Cities

Contact: cdouglas@umn.edu

Hosted by: Dr. Levi Stanley

Title:

Alkene Cyanoamidation and Aminocyanation Reactions: Discovery, Mechanism, and Applications in Alkaloid Synthesis

Abstract:

The metal-mediated activation of bonds to carbon has changed the way organic chemists approach chemical synthesis.  This presentation will focus on our work with C–C & C–N bond activation and functionalization.  Cyanoformamides are easily prepared but underused as reactants in chemical synthesis.  With palladium catalysis, the C–C bond linking the acyl and nitrile carbons can be activated, with subsequent intramolecular addition across alkenes to form the desired product through a process called cyanoamidation. Related chemistry of cyanamides, in which the N–CN bond is cleaved for alkene amino-cyanation will also be presented.  Our mechanistic work in this area elucidated the role of Lewis base and Lewis acid additives in these reaction through a combination of initial rate kinetics, natural abundance ¹³C isotope effects, control experiments, and crossover studies. For cyanoamidation, we established a linear solvation energy relationship between enantioselectivity and solvent polarity through construction of a Kamlet-Taft multiparameter solvatochromic equation.  Our mechanism-focused approach paved the way for the application of cyanoamidation in the total synthesis of the alkaloid (+)-eburnamonine.  I will present our lab’s work on applying these lessons to the madangamine alkaloids via a palladium-catalyzed C–C bond functionalization cascade reaction.

Bio:

Chris Douglas was born in Wisconsin and grew up on a farm in western Minnesota.  A first-generation college graduate, he obtained his B.S. in chemistry from the University of Minnesota – Twin Cities and his Ph.D. at the University of California, Irvine with Prof. Larry E. Overman. After postdoctoral research with Prof. Robert H. Grubbs at Caltech, he started his independent research career at his alma mater in 2007. His research focus is in two main areas: 1) discovering catalysts for the activation acyl-type carbon sigma bonds (C–H, C–C, C–O, and C–N) for the synthesis of complex molecules and 2) the synthesis and crystal engineering of conjugated molecules. Through the second research area, he collaborates with physical chemists and materials scientists to understand fundamental properties and how these molecules work in electronic devices.  His work has been recognized through NSF CAREER, DuPont Young Investigator, Cottrell Scholar awards, as well as several University of Minnesota teaching awards. Chris regularly teaches graduate level classes on organic synthesis or physical organic chemistry, undergraduate organic chemistry, or an enrollment-capped freshman seminar course titled “Chemistry in the Kitchen”.  He is the father of two children, Jack (age 16) and Cate (age 12).  He enjoys hiking in all types of weather with his wife of 21 years, Rosalind.