Efficient In Situ Regeneration of NADH Mimics by an Artificial Metalloenzyme

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• 作者：Yasunori Okamoto ; Valentin Köhler ; Caroline E. Paul ; Frank Hollmann ; Thomas R. Ward
• 刊名：ACS Catalysis
• 出版年：2016
• 出版时间：June 3, 2016
• 年：2016
• 卷：6
• 期：6
• 页码：3553-3557
• 全文大小：435K
• 年卷期：0
• ISSN：2155-5435

文摘

NADH mimics (mNADHs) have been shown to accelerate and orthogonally activate ene reductase-catalyzed reactions. However, existing regeneration methods of NAD(P)H fail for mNADHs. Catalysis with artificial metalloenzymes based on streptavidin (Sav) variants and a biotinylated iridium cofactor enable mNADH regeneration with formate. This regeneration can be coupled with ene reductase-catalyzed asymmetric reduction of α,β-unsaturated compounds, because of the protective compartmentalization of the organometallic cofactor. With 10 mol % mNAD⁺, a preparative scale reaction (>100 mg) gave full conversion with 98% ee, where TTNs reached 2000, with respect to the Ir cofactor under ambient atmosphere in aqueous medium.