Electrochemically Driven Nickel‐Catalyzed Enantioselective Hydro‐Arylation/Alkenylation of Enones

Abstract Herein, the study reports the first electrochemical nickel‐catalyzed enantioselective hydro‐arylation/alkenylation of enones in an undivided cell with low‐cost electrodes in the absence of external reductants and supporting electrolytes. Aryl bromides/iodides/triflates or alkenyl bromides a...

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Main Authors: Zenghui Ye, Weiyuan Ma, Xi Zhang, Huaqing Liu, Fengzhi Zhang
Format: Article
Language:English
Published: Wiley 2024-11-01
Series:Advanced Science
Subjects:
Online Access:https://doi.org/10.1002/advs.202405926
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author Zenghui Ye
Weiyuan Ma
Xi Zhang
Huaqing Liu
Fengzhi Zhang
author_facet Zenghui Ye
Weiyuan Ma
Xi Zhang
Huaqing Liu
Fengzhi Zhang
author_sort Zenghui Ye
collection DOAJ
description Abstract Herein, the study reports the first electrochemical nickel‐catalyzed enantioselective hydro‐arylation/alkenylation of enones in an undivided cell with low‐cost electrodes in the absence of external reductants and supporting electrolytes. Aryl bromides/iodides/triflates or alkenyl bromides are employed as electrophiles for the efficient preparation of more than 56 valuable β‐arylated/alkenylated 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 suggests that a NiI/NiIII cycle may be 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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issn 2198-3844
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spelling doaj-art-dbe3ccf4308347418d30f4056a8ef9e82025-08-20T02:58:41ZengWileyAdvanced Science2198-38442024-11-011142n/an/a10.1002/advs.202405926Electrochemically Driven Nickel‐Catalyzed Enantioselective Hydro‐Arylation/Alkenylation of EnonesZenghui Ye0Weiyuan Ma1Xi Zhang2Huaqing Liu3Fengzhi Zhang4School of Pharmacy Hangzhou Medical College Hangzhou Zhejiang 311399 ChinaSchool of Pharmacy Hangzhou Medical College Hangzhou Zhejiang 311399 ChinaSchool of Pharmacy Hangzhou Medical College Hangzhou Zhejiang 311399 ChinaSchool of Pharmacy Hangzhou Medical College Hangzhou Zhejiang 311399 ChinaSchool of Pharmacy Hangzhou Medical College Hangzhou Zhejiang 311399 ChinaAbstract Herein, the study reports the first electrochemical nickel‐catalyzed enantioselective hydro‐arylation/alkenylation of enones in an undivided cell with low‐cost electrodes in the absence of external reductants and supporting electrolytes. Aryl bromides/iodides/triflates or alkenyl bromides are employed as electrophiles for the efficient preparation of more than 56 valuable β‐arylated/alkenylated 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 suggests that a NiI/NiIII cycle may be 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.https://doi.org/10.1002/advs.202405926asymmetric synthesischiral nickel catalystselectrochemical reductive conjugate arylationelectrochemistry
spellingShingle Zenghui Ye
Weiyuan Ma
Xi Zhang
Huaqing Liu
Fengzhi Zhang
Electrochemically Driven Nickel‐Catalyzed Enantioselective Hydro‐Arylation/Alkenylation of Enones
Advanced Science
asymmetric synthesis
chiral nickel catalysts
electrochemical reductive conjugate arylation
electrochemistry
title Electrochemically Driven Nickel‐Catalyzed Enantioselective Hydro‐Arylation/Alkenylation of Enones
title_full Electrochemically Driven Nickel‐Catalyzed Enantioselective Hydro‐Arylation/Alkenylation of Enones
title_fullStr Electrochemically Driven Nickel‐Catalyzed Enantioselective Hydro‐Arylation/Alkenylation of Enones
title_full_unstemmed Electrochemically Driven Nickel‐Catalyzed Enantioselective Hydro‐Arylation/Alkenylation of Enones
title_short Electrochemically Driven Nickel‐Catalyzed Enantioselective Hydro‐Arylation/Alkenylation of Enones
title_sort electrochemically driven nickel catalyzed enantioselective hydro arylation alkenylation of enones
topic asymmetric synthesis
chiral nickel catalysts
electrochemical reductive conjugate arylation
electrochemistry
url https://doi.org/10.1002/advs.202405926
work_keys_str_mv AT zenghuiye electrochemicallydrivennickelcatalyzedenantioselectivehydroarylationalkenylationofenones
AT weiyuanma electrochemicallydrivennickelcatalyzedenantioselectivehydroarylationalkenylationofenones
AT xizhang electrochemicallydrivennickelcatalyzedenantioselectivehydroarylationalkenylationofenones
AT huaqingliu electrochemicallydrivennickelcatalyzedenantioselectivehydroarylationalkenylationofenones
AT fengzhizhang electrochemicallydrivennickelcatalyzedenantioselectivehydroarylationalkenylationofenones