Electrochemically driven Nickel-Catalyzed Enantioselective Reductive Conjugate (Hetero)Arylation of Enones
Herein, we report an electrochemical nickel-catalyzed enantioselective reductive conjugate (hetero)arylation of enones in an undivided cell with low-cost electrodes in the absence of external reductants. Aryl bromides/iodides/triflates or vinyl bromides were employed as electrophilic reagents for the efficient preparation of more than 50 valuable β-arylated ketones in a simple manner (up to 97% yield, 97% ee). With the advantages of electrochemistry, excellent functional group tolerance and late-stage modification of complex natural products and pharmaceuticals made the established protocol greener and more economic. Mechanism investigation suggest that a NiI/NiIII cycle is involved in this electro-reductive reaction rather than metal reductant driven Ni0/NiII cycle. Overall, the efficient electrochemical activation and turnover of the nickel catalyst avoid the drawbacks posed by the employment of stoichiometric amount of sensitive metal powder reductants..
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Preprint| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
chemRxiv.org - (2024) vom: 03. Apr. Zur Gesamtaufnahme - year:2024 |
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| Sprache: |
Englisch |
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| Beteiligte Personen: |
Ye, Zenghui [VerfasserIn] |
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| Links: |
Volltext [kostenfrei] |
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| doi: |
10.26434/chemrxiv-2024-zb3sh |
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| 520 | |a Herein, we report an electrochemical nickel-catalyzed enantioselective reductive conjugate (hetero)arylation of enones in an undivided cell with low-cost electrodes in the absence of external reductants. Aryl bromides/iodides/triflates or vinyl bromides were employed as electrophilic reagents for the efficient preparation of more than 50 valuable β-arylated ketones in a simple manner (up to 97% yield, 97% ee). With the advantages of electrochemistry, excellent functional group tolerance and late-stage modification of complex natural products and pharmaceuticals made the established protocol greener and more economic. Mechanism investigation suggest that a NiI/NiIII cycle is involved in this electro-reductive reaction rather than metal reductant driven Ni0/NiII cycle. Overall, the efficient electrochemical activation and turnover of the nickel catalyst avoid the drawbacks posed by the employment of stoichiometric amount of sensitive metal powder reductants. | ||
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| 700 | 1 | |a Zhang, Xi |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Huaqing |e verfasserin |4 aut | |
| 700 | 1 | |a Zhang, Fengzhi |e verfasserin |4 aut | |
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