Developing biological catalysts for chemical transformations beyond those encompassed by naturally occurring enzymes can open new opportunities for the exploitation of biocatalysis for organic synthesis. Metal-catalyzed carbene insertion into C=C double bonds and heteroatom-hydrogen bonds as well as nitrene insertion into C—H bonds represent a powerful approach for the construction of new C—C and C—heteroatom bonds in organic molecules.  In this lecture, we will present recent advances made in our laboratory toward the development of efficient and selective myoglobin-derived catalysts for promoting these types of transformations, and specifically olefin cyclopropanation, heteroatom-H bond functionalization via carbene insertion, and intramolecular C—H amination reactions. Presentation of these results will be complemented with a discussion on our current understanding and hypotheses regarding key structural features that influence the reactivity and selectivity of these hemoprotein-based catalysts.  <br/>

Carbene and nitrene transfer reactions catalyzed by engineered hemoproteins

249th National Meeting (2015)

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