The author of 《Mechanistic Studies of Fatty Acid Activation by CYP152 Peroxygenases Reveal Unexpected Desaturase Activity》 were Pickl, Mathias; Kurakin, Sara; Cantu Reinhard, Fabian G.; Schmid, Philipp; Poecheim, Alexander; Winkler, Christoph K.; Kroutil, Wolfgang; de Visser, Sam P.; Faber, Kurt. And the article was published in ACS Catalysis in 2019. Reference of Diethyl 2-methylmalonate The author mentioned the following in the article:
The majority of cytochrome P 450 enzymes (CYPs) predominantly operate as monooxygenases, but recently a class of P 450 enzymes was discovered, that can act as peroxygenases (CYP152). These enzymes convert fatty acids through oxidative decarboxylation, yielding terminal alkenes, and through α- and β-hydroxylation to yield hydroxy-fatty acids. Bioderived olefins may serve as biofuels, and hence understanding the mechanism and substrate scope of this class of enzymes is important. In this work, we report on the substrate scope and catalytic promiscuity of CYP OleTJE (CYP152L1) and two of its orthologues from the CYP152 family, utilizing α-monosubstituted branched carboxylic acids. We identify α,β-desaturation as an unexpected dominant pathway for CYP OleTJE with 2-methylbutyric acid. To rationalize product distributions arising from α/β-hydroxylation, oxidative decarboxylation, and desaturation depending on the substrate’s structure and binding pattern, a computational study was performed based on an active site complex of CYP OleTJE containing the heme cofactor in the substrate binding pocket and 2-methylbutyric acid as substrate. It is shown that substrate positioning determines the accessibility of the oxidizing species (Compound I) to the substrate and hence the regio- and chemoselectivity of the reaction. Furthermore, the results show that, for 2-methylbutyric acid, α,β-desaturation is favorable because of a rate-determining α-hydrogen atom abstraction, which cannot proceed to decarboxylation. Moreover, substrate hydroxylation is energetically impeded due to the tight shape and size of the substrate binding pocket. The results came from multiple reactions, including the reaction of Diethyl 2-methylmalonate(cas: 609-08-5Reference of Diethyl 2-methylmalonate)
Diethyl 2-methylmalonate(cas: 609-08-5) belongs to aliphatic hydrocarbons. Aliphatic hydrocarbons belong to the most abundant fraction in crude oil. Aliphatics molecules are linear or branched open-chain structures such as n-alkanes, isoalkanes, cycloalkanes (naphthenes), terpenes and steranes.Reference of Diethyl 2-methylmalonate
Referemce:
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics