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Published December 18, 2019 | Accepted Version + Submitted + Supplemental Material
Journal Article Open

Nitrene Transfer Catalyzed by a Non-Heme Iron Enzyme and Enhanced by Non-Native Small-Molecule Ligands

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.

Additional Information

© 2019 American Chemical Society. Received: October 28, 2019; Published: December 2, 2019. This work was supported by the National Science Foundation (NSF) Division of Molecular and Cellular Biosciences (grant MCB-1513007). N.W.G., A.M.K., and R.K.Z. acknowledge support from the U.S. National Institutes of Health (NIH) training grants NIH T32 GM07616 (N.W.G.) and NIH T32 GM112592 (A.M.K., R.K.Z.) and NSF Graduate Research Fellowship DGE-1144469 (A.M.K., R.K.Z.). We thank Sabine Brinkmann-Chen for critical reading of the manuscript and Noah P. Dunham, S. B. Jennifer Kan, and Benjamin J. Levin for helpful discussions. We thank Professor Hans Renata and Professor Harry Gray for generously sharing plasmids. Author Contributions: N.W.G. and A.M.K. contributed equally. The authors declare the following competing financial interest(s): A provisional patent, on which N.W.G., A.M.K., and R.K.Z. are inventors, has been filed through the California Institute of Technology based on the results presented here.

Attached Files

Accepted Version - jacs.9b11608_accepted.pdf

Accepted Version - nihms-1062404.pdf

Submitted - EFE_Manuscript_20191028.pdf

Supplemental Material - ja9b11608_si_001.pdf

Supplemental Material - ja9b11608_si_002.xlsx

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Additional details

Created:
August 19, 2023
Modified:
October 18, 2023