The Remarkable Impact of "Nitrene"-Precursor Structure on Reaction Outcome in Rh-Catalyzed Olefin Amination Reactions

Abstract: Chiral amines are important building blocks in pharmaceutical, agrochemical and natural products chemistry. Transition metal catalyzed enantioselective amination of readily available olefin starting materials represents a particularly important strategy to access this important class of molecules. In this lecture we present the development of a novel planar chiral catalyst platform and describe the remarkable influence of the aminating reagent on reaction outcome. Three different “nitrene” precursor reagents are shown to provide three different reaction outcomes, using the same catalyst and the same substrates, and the concomitant development of broadly applicable allylic amination, aziridination, and olefin aryl-amination reactions will be showcased. Computational investigations provide mechanistic insight into the subtle control factors leading to the divergent reaction outcomes and provide predictive insight into the different reactivities observed between indenyl and Cp ligands on the rhodium catalyst.

Biography: Simon was born in Auckland, New Zealand. Having spent time growing up in both New Zealand and Singapore, he received his B.Sc. degree in Chemistry and Biochemistry at the University of Auckland in 1997. He then moved to the U.K. and completed his Ph.D. in 2002 studying the synthesis of the aplyronine family of natural products under the direction of Professor Ian Paterson at the University of Cambridge. After three years as a postdoctoral fellow investigating nickel catalyzed cross-coupling reactions and organocatalytic approaches to diazonamide A with Professor David MacMillan at the California Institute of Technology, Simon joined the faculty at Emory University in the fall of 2005. Today his research interests revolve around the development of new organometallic catalysts and synthetic methodology, and the implementation of these technologies to impact both drug discovery and materials science.