Nitrile Anions: Unmasking Fundamental Reactivity

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Professor Fleming and his coworkers have discovered that cyclic nitrile anions generated in tetrahydrofuran or toluene can be selectively alkylated intramolecularly to generate trans- and cis-decalins, respectively. They will apply this discovery to the syntheses of two decalin containing clerodane natural products. With the help of his collaborator, Professor Madura, computational modelling of the structures of the metallated nitriles which participate in these reactions will be investigated. Lastly, the PI will generate chiral metallated nitriles and investigate their enantioselective intramolecular alkylation.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Fraser F. Fleming of the Department of Chemistry at Duquesne University. Professor Fleming along with his collaborator, Professor Jeffrey D. Madura, and their students will study the structures and reaction chemistry of a class of molecules known as nitrile anions. Intramolecular carbon-carbon bond forming reactions of these nitrile anions will be used to construct two naturally occurring diterpenes, strigillanoic acid and epi-strigillanoic acid. Nitriles which can be metallated on the carbon next to the nitrile functional group will then be used in enantioselective carbon-carbon bond forming reactions called intramolecular alkylation reactions. These alkylation reactions produce cyclic molecules which are chiral (have two nonsuperimposable mirror images) and make only one of the two possible forms (a single enantiomer). Development of this family of reactions is one of the most important problems facing the pharmaceutical industry today. Students trained during the course of this work will gain skills in computational chemistry and organic synthesis. These skills are needed by the pharmaceutical and speciality chemicals industries.