METALATED NITRILES: UNMASKING FUNDAMENTAL REACTIVITY

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In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Fraser F. Fleming of the Department of Chemistry at Duquesne University will explore fundamentally new reactions of metalated nitriles. Preliminary results demonstrate the viability of several new reactivity patterns for alkylating alkenes, aromatics, and creating medium-sized carbocycles. Studies to expand and develop these forays into robust synthetic methods will be undertaken. Asymmetric alkylations of zincated and magnesiated nitriles will be performed through a combination of screening and mechanistic probes to address one of the most difficult challenges in the field: stereoselective alkylation of a chiral, metalated nitrile.The research is likely to lead to new methods for stereoselectively assembling hindered, quaternary centers. Fields as diverse as medicine and materials rely on exactly this type of robust chemistry. The nitrile-based arylation is particularly well suited to the synthesis of several nitrile-containing pharmaceuticals and drug leads because the method uses an inexpensive, abundant copper catalyst rather than palladium catalysts that are currently required for the same transformation.Three broader impacts will be reached through this research: institutional development, elevation of nitrile chemistry, and student training. As a teacher-scholar institution a strong emphasis is placed on undergraduate and graduate mentoring while pursuing research excellence. In this context, the student research will, in part, be guided by a post-doctoral associate with reciprocal mentoring from the PI to the post-doctoral associate.