Catalytic, Regioselective Functionalization of Alkanes and Arenes

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This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Dr. John F. Hartwig of Yale University to understand the efficient cleavage and functionalization of alkane and arene C-H bonds by borane reagents and metal boryl intermediates and to exploit a new approach to alkane and arene functionalization. The project aims to understand how boryl groups create metal centers that are unusually reactive toward C-H bond cleavage and how the intermediates from C-H bond activation create functionalized products. The synthetic potential for reactions with functionalized substrates and polyolefins will also be evaluated. Specifically, rhodium catalysts modified with anionic ligands other than substituted cyclopentadienyl groups and ruthenium catalysts with pentamethylcyclopentadienyl ligands will be studied to identify the features of the catalyst structure that create activity for the functionalization of alkanes and arenes. As the borylation of small alkanes can be extended to the borylation of protected, functionalized substrates and to the borylation of polyolefins, these reactions will be developed as an important step toward conducting selective functionalization of methyl groups in a complex molecule and toward generating prototype polyolefins that contain a variety of functional groups at the termini of sidechains. Directly transforming hydrocarbon bonds into useful chemicals and pharmaceuticals is a goal of both laboratory and economic significance. In particular, the conversion of alkanes to linear alcohols, amines and carboxylic acids is a prominent goal in synthetic organic chemistry. This work capitalizes on Hartwig's discovery of a catalytic system that generates linear functionalized products from alkanes in only two steps. This project also integrates research into a broader educational experience for both students and postdocs and provides them with training in advanced catalytic methods.