Elucidating the Reaction Pathway of Decarboxylation-Assisted Olefination Catalyzed by a Mononuclear Non-Heme Iron Enzyme
journal contributionposted on 30.10.2018, 00:00 by Cheng-Ping Yu, Yijie Tang, Lide Cha, Sergey Milikisiyants, Tatyana I. Smirnova, Alex I. Smirnov, Yisong Guo, Wei-chen Chang
Installation of olefins into molecules is a key transformation in organic synthesis. The recently discovered decarboxylation-assisted olefination in the biosynthesis of rhabduscin by a mononuclear non-heme iron enzyme (P.IsnB) represents a novel approach in olefin construction. This method is commonly employed in natural product biosynthesis. Herein, we demonstrate that a ferryl intermediate is used for C–H activation at the benzylic position of the substrate. We further establish that P.IsnB reactivity can be switched from olefination to hydroxylation using electron-withdrawing groups appended on the phenyl moiety of the analogues. These experimental observations imply that a pathway involving an initial C–H activation followed by a benzylic carbocation species or by electron transfer coupled β-scission is likely utilized to complete CC bond formation.
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electron-withdrawing groupsbenzylic positionbenzylic carbocation speciespathwaynovel approachIsnB reactivityanalogueferrylolefinshydroxylationactivationMononuclear Non-Heme Iron Enzyme Installationtransformationnon-heme iron enzymephenyl moietyproduct biosynthesismoleculeElucidatingformationelectron transferβ- scissionDecarboxylation-Assisted Olefination CatalyzedReaction Pathwaysubstrateolefin constructionHereinmethodrhabduscindecarboxylation-assisted olefinationbond