Efficient Nicotinamide Adenine Dinucleotide Regeneration with aRhodium-Carbene Catalyst and Isolation of a Hydride Intermediate

被引：10

作者：

Ganesan, Vinothkumar ^{[1
]}

Kim, Jennifer Juhyun ^{[1
]}

Shin, Jeongcheol ^{[2
]}

Park, Kiyoung ^{[2
]}

Yoon, Sungho ^{[1
]}

机构：

[1] Chung Ang Univ, Dept Chem, Seoul 06974, South Korea

[2] Korea Adv Inst Sci & Technol, Dept Chem, Daejeon 34141, South Korea

来源：

INORGANIC CHEMISTRY | 2022年 / 61卷 / 15期

基金：

新加坡国家研究基金会;

关键词：

BIOORGANOMETALLIC CHEMISTRY; REGIOSELECTIVE REDUCTION; RHODIUM(III) COMPLEXES; NAD(P)-DEPENDENT OXIDOREDUCTASES; ENANTIOSELECTIVE REDUCTION; ELECTROCHEMICAL PROPERTIES; POTENTIAL APPLICATIONS; MECHANISTIC ASPECTS; CRYSTAL-STRUCTURES; NADH REGENERATION;

D O I：

10.1021/acs.inorgchem.2c00059

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Regeneration of nicotinamide adenine dinucleotide(NADH) has been the primary interest in thefield of enzymatictransformation, especially associating oxidoreductases given thestoichiometric consumption. The synthesized carbene-ligatedrhodium complex [(eta 5-Cp*)Rh(MDI)Cl]+[Cp*= pentamethyl-cyclopentadienyl; MDI = 1,1 '-methylenebis(3,3 '-dimethylimidazo-lium)] acts as an exceptional catalyst in the reduction of NAD+toNADH with a turnover frequency of 1730 h-1, which is over twicethat of the higher catalytic activity of the commercially availablecatalyst [Cp*Rh(bpy)Cl]+(bpy = 2,2'-bipyridine). Offsetting thecontentious atmosphere currently taking place over the specificintermediate of the NADH regeneration, this study presentspivotal evidence of a metal hydride intermediate with abis(carbene) ligand: a stable form of the rhodium hydride intermediate, [(eta 5-Cp*)Rh(MDI)H]+, was isolated and fullycharacterized. This enables thorough insight into the possible mechanism and exact intermediate structure in the NAD+reductionprocess

引用

页码：5683 / 5690

页数：8

共 67 条

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