The work described is focused on the development of biosynthetic oxygenases as synthetically useful tools for the selective C-H oxidation of substrates ranging from small molecules to complex biologically active molecules. Direct C-H oxidation of substrates, available from natural or synthetic sources, provides access to compounds with new or improved pharmaceutical properties. Historically, efforts to derivatize complex molecules have been limited to sites within the molecule that have a preexisting functional handle; however, the field of C-H activation has changed the rules of complex molecule synthesis, redefining C-H bonds as precursors to C-O, C-N, C-C and C-halogen bonds. Despite the growing number of organometallic methods for C-H oxidation, achievement of regio- and stereoselective C-H functionalization on the intricate landscape of complex compounds remains one of the great challenges in organic synthesis.The work described leverages tertiary amines, capable of forming salt bridges in the enzyme active site, as directing groups for the oxidation of remote C-H bonds. This strategy has been successful for the regio- and stereoselective oxidation of C-H bonds contained within simple substrates, such as menthol, as well as complex natural products.

Bioinspired approaches to C-H bond oxidation

246th National Meeting (2013)

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