CuII‐Containing 1‐Aminocyclopropane Carboxylic Acid Oxidase Is an Efficient Stereospecific Diels–Alderase. (5th September 2019)

• Record Type: Journal Article
• Authors: Ghattas, Wadih; Dubosclard, Virginie; Tachon, Sybille; Beaumet, Morane; Guillot, Régis; Réglier, Marius; Simaan, A. Jalila; Mahy, Jean‐Pierre
• Is Part Of: Angewandte Chemie. Volume 131:Number 41(2019)
• Page Start: 14747
• Page End: 14751
• Publication Date: 2019-09-05
• Subjects: Enzymkatalyse -- Diels-Alder-Reaktionen -- Künstliche Enzyme; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201909407
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: In the context of developing ecofriendly chemistry, artificial enzymes are now considered as promising tools for synthesis. They are prepared in particular with the aim to catalyze reactions that are rarely, if ever, catalyzed by natural enzymes. We discovered that 1‐aminocyclopropane carboxylic acid oxidase reconstituted with Cu II served as an efficient artificial Diels–Alderase. The kinetic parameters of the catalysis of the cycloaddition of cyclopentadiene and 2‐azachalcone were determined ( K M =230 μm, k app =3 h −1 ), which gave access to reaction conditions that provided quantitative yield and >99 % ee of the ( 1S, 2R, 3R, 4R ) product isomer. This unprecedented performance was rationalized by molecular modeling as only one docking pose of 2‐azachalcone was possible in the active site of the enzyme and this was the one that leads to the ( 1S, 2R, 3R, 4R ) product isomer. Abstract : Die Natur ein Stück justiert : Künstliche Enzyme katalysieren Reaktionen, die nur selten oder gar nicht von natürlichen Enzymen durchgeführt werden. Modifizierte 1‐Aminocyclopropancarbonsäure‐Oxidase, die Cu II enthält, fungiert als Diels‐Alderase ( K M =230 μm, k app =3 h −1 ) und liefert Reaktionsprodukte in quantitativen Ausbeuten mit >99 % ee .