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6659029 
Journal Article 
Olefin Cyclopropanation via Carbene Transfer Catalyzed by Engineered Cytochrome P450 Enzymes 
Coelho, PS; Brustad, EM; Kannan, A; Arnold, FH; , 
2013 
1 
Science
ISSN: 0036-8075
EISSN: 1095-9203 
AMER ASSOC ADVANCEMENT SCIENCE 
WASHINGTON 
307-310 
23258409 
WOS:000313622000040 
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 P450(BM3) 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 the catalysis of synthetically important reactions not previously observed in nature.