How do aldehyde side products occur during alkene epoxidation by cytochrome P450? Theory reveals a state-specific multi-state scenario where the high-spin component leads to all side products

Journal of Inorganic Biochemistry
Sam P de VisserSason Shaik

Abstract

A theoretical study of alkene epoxidation, by the high-valent iron-oxo species (Compound I) of cytochrome P450, reveals a multi-state scenario in which the different products are generated in a state specific manner. All the low-spin doublet state processes are effectively concerted epoxide producing pathways. By contrast, all the high-spin quartet processes are stepwise and either lead to epoxide that does not conserve the isomeric identity of the alkene (cis or trans), or/and to by-products such as suicidal complexes and aldehydes. The product/state inventory is the following: (a) The epoxide with conserved alkene stereochemistry is generated from the low-spin doublet states of Compound I in a nonsynchronous but effectively concerted pathways that involve carbon radical (with Fe(III) and Fe(IV)) and cationic intermediates. (b) The epoxide with scrambled alkene stereochemistry is obtained from the quartet high-spin radical intermediate (with Fe(IV)). (c) The suicidal complex, with a C-N bond between the alkene and the porphyrin, is obtained from the high-spin cationic state that possesses one electron in the sigma xy* orbital (the antibonding Fe-N orbital made from dxy and nitrogen sigma-hybrids). (d) The aldehyde by-product i...Continue Reading

Citations

Jan 29, 2013·Applied and Environmental Microbiology·Shirley F NishinoJim C Spain
Dec 19, 2015·Food and Chemical Toxicology : an International Journal Published for the British Industrial Biological Research Association·Alexander T Cartus, Dieter Schrenk
Feb 16, 2015·The Journal of Chemical Physics·Justin E Elenewski, John C Hackett
Mar 24, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Lin-Lin ZhangChi-Ming Che
Feb 22, 2005·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Devesh KumarSason Shaik
Oct 11, 2008·Chemistry, an Asian Journal·Tetsuya K Yanai, Seiji Mori
Mar 14, 2009·Chemistry : a European Journal·Tetsuya K Yanai, Seiji Mori
Oct 14, 2017·Science·Stephan C HammerFrances H Arnold

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