Transition Metal-Catalyzed Nitrogenation of Hydrocarbons

University Of Oklahoma Norman Campus, Norman OK

Investigators

Abstract

The importance of amines and N-heterocycles, both as synthetic intermediates and as end-products, makes the genesis of new, efficient and selective C-N bond-forming reactions an important objective. Transition metal-mediated reactions which selectively produce new C-C, C-O and C-H bonds from C-C unsaturation have dramatically increased the power of organic synthesis, but the potential of transition metals to facilitate corresponding C-N bond formation (nitrogenation) is just beginning to be realized. This project responds to a dual need: 1) for new selective methods for the synthesis of organonitrogen compounds and 2) for new understanding of the reactivity of organonitrogen fragments coordinated to metal centers. Two recently discovered reactions are targeted for detailed study during the project period: 1) organometal-catalyzed allylic aminations by nitroorganics; and 2) reductive annulation of nitro- and nitrosoarenes with alkynes to produce indoles and other heterocycles. Mechanistic analysis will elucidate the nature of the active aminating species involved, while synthetic studies will provide access to a number of important nitrogen-containing products, including potential precursors for the indole alkaloids. Numerous organic compounds of biological or medicinal importance contain nitrogen atoms. The development of efficient, selective, and catalytic methods for the introduction of nitrogen into organic molecules remains a significant research objective. Professor Kenneth M. Nicholas, of the Department of Chemistry and Biochemistry at the University of Oklahoma (Norman Campus), is supported by the Organic and Macromolecular Chemistry Program for his studies of the nitrogenation of hydrocarbons. Professor Nicholas has discovered a series of unusual metal-catalyzed reactions, each of which provides a novel and direct route to valuable nitrogen-containing organic products. The metal-mediated processes leading to these compounds proceed from readily available starting materials and are expected to be highly selective, versatile, and complementary or superior to existing methods. New efficient, economical, and environmentally-friendly nitrogenation processes for the chemical and pharmaceutical industries also could result. This project also will serve as an effective vehicle for the education and technical training of undergraduate, graduate and postdoctoral students in the fundamentally and technologically critical areas of chemical synthesis and catalysis.