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Olefin Cyclopropanation via Carbene Transfer Catalyzed by Engineered Cytochrome P450 Enzymes

Science  20 Dec 2012:

DOI: 10.1126/science.1231434

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Abstract

Transition metal-catalyzed transfers of carbenes, nitrenes and oxenes are powerful methods for functionalizing C=C and C–H bonds. Nature has evolved a diverse toolbox for oxene transfers, as exemplified by the myriad monooxygenation reactions catalyzed by cytochrome P450 enzymes. The isoelectronic carbene transfer to olefins, a widely used C–C bond forming reaction in organic synthesis, has no biological counterpart. Here, we report engineered variants of cytochrome P450BM3 that catalyze highly diastereo- and enantioselective cyclopropanation of styrenes from diazoester reagents via putative carbene transfer. This work highlights the capacity to adapt existing enzymes for catalysis of synthetically important reactions not previously observed in Nature.

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