Nitrene Transfer Catalyzed by a Non-Heme Iron Enzyme and Enhanced by Non-Native Small-Molecule Ligands
Transition-metal catalysis is a powerful tool for the construction of chemical bonds. Here we show that Pseudomonas savastanoi ethylene-forming enzyme, a non-heme iron enzyme, can catalyze olefin aziridination and nitrene C–H insertion, and that these activities can be improved by directed evolution...
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| Published in | Journal of the American Chemical Society Vol. 141; no. 50; pp. 19585 - 19588 |
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| Main Authors | , , , |
| Format | Journal Article |
| Language | English |
| Published |
United States
American Chemical Society
18.12.2019
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| Subjects | |
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| Abstract | Transition-metal catalysis is a powerful tool for the construction of chemical bonds. Here we show that Pseudomonas savastanoi ethylene-forming enzyme, a non-heme iron enzyme, can catalyze olefin aziridination and nitrene C–H insertion, and that these activities can be improved by directed evolution. The non-heme iron center allows for facile modification of the primary coordination sphere by addition of metal-coordinating molecules, enabling control over enzyme activity and selectivity using small molecules. |
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| AbstractList | Transition-metal catalysis is a powerful tool for the construction of chemical bonds. Here we show that Pseudomonas savastanoi ethylene-forming enzyme, a non-heme iron enzyme, can catalyze olefin aziridination and nitrene C–H insertion, and that these activities can be improved by directed evolution. The non-heme iron center allows for facile modification of the primary coordination sphere by addition of metal-coordinating molecules, enabling control over enzyme activity and selectivity using small molecules. Transition-metal catalysis is a powerful tool for the construction of chemical bonds. Here we show that ethylene-forming enzyme, a non-heme iron enzyme, can catalyze olefin aziridination and nitrene C-H insertion, and that these activities can be improved by directed evolution. The non-heme iron center allows for facile modification of the primary coordination sphere by addition of metal-coordinating molecules, enabling control over enzyme activity and selectivity using small molecules. Transition-metal catalysis is a powerful tool for the construction of chemical bonds. Here we show that Pseudomonas savastanoi ethylene-forming enzyme, a non-heme iron enzyme, can catalyze olefin aziridination and nitrene C-H insertion, and that these activities can be improved by directed evolution. The non-heme iron center allows for facile modification of the primary coordination sphere by addition of metal-coordinating molecules, enabling control over enzyme activity and selectivity using small molecules.Transition-metal catalysis is a powerful tool for the construction of chemical bonds. Here we show that Pseudomonas savastanoi ethylene-forming enzyme, a non-heme iron enzyme, can catalyze olefin aziridination and nitrene C-H insertion, and that these activities can be improved by directed evolution. The non-heme iron center allows for facile modification of the primary coordination sphere by addition of metal-coordinating molecules, enabling control over enzyme activity and selectivity using small molecules. Transition-metal catalysis is a powerful tool for the construction of chemical bonds. Here we show that Pseudomonas savastanoi ethylene-forming enzyme ( Ps EFE), a non-heme iron enzyme, can catalyze olefin aziridination and nitrene C–H insertion, and that these activities can be improved by directed evolution. The non-heme iron center allows for facile modification of the primary coordination sphere by addition of metal-coordinating molecules, enabling control over enzyme activity and selectivity using small molecules. |
| Author | Knight, Anders M Arnold, Frances H Goldberg, Nathaniel W Zhang, Ruijie K |
| AuthorAffiliation | Division of Chemistry and Chemical Engineering Division of Biology and Bioengineering |
| AuthorAffiliation_xml | – name: Division of Chemistry and Chemical Engineering – name: Division of Biology and Bioengineering – name: Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, MC 210-41, Pasadena, California 91125, United States – name: Division of Biology and Bioengineering, California Institute of Technology, 1200 East California Boulevard, MC 210-41, Pasadena, California 91125, United States |
| Author_xml | – sequence: 1 givenname: Nathaniel W orcidid: 0000-0003-0201-8856 surname: Goldberg fullname: Goldberg, Nathaniel W – sequence: 2 givenname: Anders M orcidid: 0000-0001-9665-8197 surname: Knight fullname: Knight, Anders M – sequence: 3 givenname: Ruijie K orcidid: 0000-0002-7251-5527 surname: Zhang fullname: Zhang, Ruijie K – sequence: 4 givenname: Frances H orcidid: 0000-0002-4027-364X surname: Arnold fullname: Arnold, Frances H email: frances@cheme.caltech.edu |
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| Cites_doi | 10.1021/jacs.7b06186 10.1038/nchembio.1438 10.1073/pnas.1617760114 10.1080/10409230490440541 10.1146/annurev-biochem-061516-044724 10.1021/cs400893n 10.1021/jacs.8b13906 10.1016/0006-291X(92)91081-Z 10.1038/nchembio.186 10.1021/acscentsci.5b00056 10.1038/s41589-019-0355-x 10.1021/cr9500390 10.1038/nchem.2783 10.1021/acs.biochem.6b00890 10.1016/j.copbio.2017.06.005 10.1002/anie.201304401 10.1021/jacs.8b02769 |
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| Snippet | Transition-metal catalysis is a powerful tool for the construction of chemical bonds. Here we show that Pseudomonas savastanoi ethylene-forming enzyme, a... Transition-metal catalysis is a powerful tool for the construction of chemical bonds. Here we show that ethylene-forming enzyme, a non-heme iron enzyme, can... Transition-metal catalysis is a powerful tool for the construction of chemical bonds. Here we show that Pseudomonas savastanoi ethylene-forming enzyme ( Ps... |
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| SubjectTerms | Alkenes - chemistry aminocyclopropanecarboxylate oxidase Aziridines - chemistry Biocatalysis catalytic activity chemical bonding directed evolution Directed Molecular Evolution enzyme activity iron Ligands Models, Molecular Nonheme Iron Proteins - chemistry Nonheme Iron Proteins - genetics Nonheme Iron Proteins - metabolism olefin Protein Conformation Pseudomonas - enzymology Pseudomonas syringae pv. savastanoi |
| Title | Nitrene Transfer Catalyzed by a Non-Heme Iron Enzyme and Enhanced by Non-Native Small-Molecule Ligands |
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