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. 2018 Feb 12;57(7):1831-1835.
doi: 10.1002/anie.201710567. Epub 2018 Jan 16.

Insights into the Desaturation of Cyclopeptin and its C3 Epimer Catalyzed by a non-Heme Iron Enzyme: Structural Characterization and Mechanism Elucidation

Hsuan-Jen Liao  1 , Jikun Li  2 , Jhih-Liang Huang  3 , Madison Davidson  3 , Igor Kurnikov  2 , Te-Sheng Lin  1 , Justin L Lee  2 , Maria Kurnikova  2 , Yisong Guo  2 , Nei-Li Chan  1 , Wei-Chen Chang  3
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Insights into the Desaturation of Cyclopeptin and its C3 Epimer Catalyzed by a non-Heme Iron Enzyme: Structural Characterization and Mechanism Elucidation

Hsuan-Jen Liao et al. Angew Chem Int Ed Engl. .

Abstract

AsqJ, an iron(II)- and 2-oxoglutarate-dependent enzyme found in viridicatin-type alkaloid biosynthetic pathways, catalyzes sequential desaturation and epoxidation to produce cyclopenins. Crystal structures of AsqJ bound to cyclopeptin and its C3 epimer are reported. Meanwhile, a detailed mechanistic study was carried out to decipher the desaturation mechanism. These findings suggest that a pathway involving hydrogen atom abstraction at the C10 position of the substrate by a short-lived FeIV -oxo species and the subsequent formation of a carbocation or a hydroxylated intermediate is preferred during AsqJ-catalyzed desaturation.

Keywords: C−C bond formation; carbocations; desaturation; enzyme mechanisms; viridicatin.

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