The Chemical Synthesis Program in the Division of Chemistry supports the work of Professor Gregory R. Cook at North Dakota State University to develop new synthetic methods for the asymmetric synthesis of chiral amines and alcohols. In particular the project will investigate novel enantioselective allylation reactions of carbon-nitrogen and carbon-oxygen double bonds mediated by the environmentally friendly metals indium and bismuth. Enantioselective catalytic allylation is a highly desired route for the preparation of chiral building blocks that can be utilized in the preparation of biologically active small molecule pharmaceuticals and tools for biological sciences. This project will develop highly catalytic enantioselective allylation of ketimines mediated by indium. Additionally, allylation of ketones mediated by bismuth metal in the presence of chiral bismuth catalysts will be developed. The purported asymmetric catalysts for both of these processes will be isolated and characterized to provide insight for future directions for the generation of environmentally benign asymmetric methods.
Selective chemical reactions that can be accomplished with minimal waste using non-toxic catalysts and reagents will allow for new greener chemical processes for future environmentally sustainable technologies. This project will provide research experiences for undergraduate students, graduate students and postdoctoral associates in the chemical sciences. In particular, undergraduate students early in their college careers (freshmen and sophomores) will benefit from this research experience. Statistics show that students engaged earlier in their college experience have a higher probability of continuing on to a career in science. This project will directly aid the goals of NSF and the Country to increase human resources in sciences.
The synthesis of organic chemicals for the preparation of medicines and materials has long demanded high energy consumption, the use of toxic reagents and catalysts, the production of toxic waste byproducts and the use of large quantities of solvents derived from petroleum products. For a sustainable future, there is a critical need for more efficient chemical processes that are environmentally benign. At the same time it is important to control the selectivity of chemical reactions which has been problematic. Toward the goal of understanding the fundamental mechanisms of organic reactions that will allow the devleopment of greener processes for use in industry, we have investigated a variety of aspects of synthetic organic methodology to address these problems. In particular we have: 1) developed new reactions to selectively build molecules that will proceed with high efficiency in biorenewable solvents including methanol (from plant sources) and water. 2) developed highly selective carbon-carbon bond formation reactions utilizing non-toxic metals (Indium and Bismuth) that allow chemists to synthesize new medicines. 3) shown for the first time that a reaction that previously required an excess of metal reagents can be accomplished using catalytic amounts of the same metal. 4) developed a deeper understanding of the underlying mechanisms of these new carbon-carbon bond forming reactions that will allow other scientists to advance other fields of organic synthesis. 5) discovered green methods without high energy requirements for organic synthesis that has the potential to be scaled up to production size with lessened environmental impact. 6) showcased our new methodology in the synthesis of natural products with profound biological activites that have the potential to develop into new medicines. 7) trained a new generation of scientists who have pursued careers in chemsitry and/or medicine.
