Chiral and Regenerable NAD(P)H Models Enabled Biomimetic Asymmetric Reduction: Design, Synthesis, Scope, and Mechanistic Studies
| Autor: | Yong-Gui Zhou, Gen Luo, Jie Wang, Zi-Biao Zhao, Zhou-Hao Zhu, Yanan Zhao, Yi Luo |
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| Rok vydání: | 2019 |
| Předmět: |
inorganic chemicals
Molecular Structure 010405 organic chemistry Chemistry Hydride organic chemicals Organic Chemistry chemistry.chemical_element Stereoisomerism 010402 general chemistry NAD 01 natural sciences Combinatorial chemistry Transition state Catalysis 0104 chemical sciences Ruthenium Biomimetics NAD+ kinase Lewis acids and bases Enantiomeric excess Brønsted–Lowry acid–base theory |
| Zdroj: | The Journal of organic chemistry. 85(4) |
| ISSN: | 1520-6904 |
| Popis: | The coenzyme NAD(P)H plays an important role in electron as well as proton transmission in the cell. Thus, a variety of NAD(P)H models have been involved in biomimetic reduction, such as stoichiometric Hantzsch esters and achiral regenerable dihydrophenantheridine. However, the development of a general and new-generation biomimetic asymmetric reduction is still a long-term challenge. Herein, a series of chiral and regenerable NAD(P)H models with central, axial, and planar chiralities have been designed and applied in biomimetic asymmetric reduction using hydrogen gas as a terminal reductant. Combining chiral NAD(P)H models with achiral transfer catalysts such as Bronsted acids and Lewis acids, the substrate scope could be also expanded to imines, heteroaromatics, and electron-deficient tetrasubstituted alkenes with up to 99% yield and 99% enantiomeric excess (ee). The mechanism of chiral regenerable NAD(P)H models was investigated as well. Isotope-labeling reactions indicated that chiral NAD(P)H models were regenerated by the ruthenium complex under hydrogen gas first, and then the hydride of NAD(P)H models was transferred to unsaturated bonds in the presence of transfer catalysts. In addition, density functional theory calculations were also carried out to give further insight into the transition states for the corresponding transfer catalysts. |
| Databáze: | OpenAIRE |
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