Biocatalytic Carbene and Nitrene Transfer Reactions

Transition metal catalyzed carbene and nitrene transfer reactions represent powerful transformations for the formation of new carbon-carbon and carbon-heteroatom bonds. Historically restricted to the realm of chemocatalysis, this class of transformations has recently become accessible through enzymatic catalysis using heme-dependent enzymes and proteins. This Chapter surveys advances in the discovery and development of hemoprotein-based biocatalysts for asymmetric carbene and nitrene transfer reactions, including olefin cyclopropanation, heteroatom-hydrogen bond carbene insertion, and C–H amination and alkylation. Expansion of the reaction scope and modulation of the chemo-, regio- and stereoselectivity of these systems via protein engineering have provided new opportunities for asymmetric catalysis and organic synthesis.