Electrocatalytic N-C-N coupling over a hierarchically ordered open single-atom superstructure toward organonitrogen...

Area of Science:

• Catalysis
• Materials Science
• Organic Synthesis

Background:

• Conventional chemosynthesis for C-N and N-C-N bonds is often energy-intensive and unsustainable.
• Developing economical and eco-friendly alternatives for synthesizing organonitrogen compounds is crucial.

Purpose of the Study:

• To explore a novel electrocatalyst for efficient N-C-N coupling.
• To demonstrate the synthesis of valuable organonitrogen compounds using electrochemistry.
• To investigate the reaction mechanism for N-C-N bond formation.

Main Methods:

• Fabrication of a hierarchically ordered N-doped carbon superstructure with isolated three-coordinated Zn single-atom sites.
• Electrocatalytic N-C-N coupling using methanol and amines.
• Cascade synthesis involving electrochemically generated intermediates.
• In situ spectroscopic characterization and computational calculations.

Main Results:

• The catalyst achieved high Faradaic efficiency (77%) and selectivity (96%) for N,N,N',N'-tetramethyldiaminomethane synthesis at 0.8 V.
• A cascade synthesis yielded organonitrogen compounds, including the anti-tumor drug topotecan hydrochloride (95% yield).
• Under-coordinated Zn-N3 sites were identified as crucial for stabilizing key intermediates (*CH2O).

Conclusions:

• The developed catalyst offers an economical and sustainable route for N-C-N bond formation.
• This electrocatalytic approach enables the synthesis of complex organonitrogen compounds with potential pharmaceutical applications.
• The study elucidates the catalytic mechanism, paving the way for further catalyst design.