Paired electrolysis-enabled nickel-catalyzed enantioselective reductive cross-coupling between α-chloroesters and aryl bromides.
Dong LiuZhao-Ran LiuZhen-Hua WangCong MaSimon HerbertHartmut SchirokTian-Sheng MeiPublished in: Nature communications (2022)
Electrochemical asymmetric catalysis has emerged as a sustainable and promising approach to the production of chiral compounds and the utilization of both the anode and cathode as working electrodes would provide a unique approach for organic synthesis. However, precise matching of the rate and electric potential of anodic oxidation and cathodic reduction make such idealized electrolysis difficult to achieve. Herein, asymmetric cross-coupling between α-chloroesters and aryl bromides is probed as a model reaction, wherein alkyl radicals are generated from the α-chloroesters through a sequential oxidative electron transfer process at the anode, while the nickel catalyst is reduced to a lower oxidation state at the cathode. Radical clock studies, cyclic voltammetry analysis, and electron paramagnetic resonance experiments support the synergistic involvement of anodic and cathodic redox events. This electrolytic method provides an alternative avenue for asymmetric catalysis that could find significant utility in organic synthesis.
Keyphrases
- electron transfer
- reduced graphene oxide
- gold nanoparticles
- ion batteries
- ionic liquid
- solid state
- visible light
- molecular dynamics simulations
- risk assessment
- energy transfer
- human health
- mass spectrometry
- case control
- hydrogen peroxide
- data analysis
- molecularly imprinted
- metal organic framework
- liquid chromatography
- oxide nanoparticles