General and selective nickel-electrocatalyzed cross-electrophile C*(sp²)-C(sp²) coupling

Area of Science:

• Organic Chemistry
• Synthetic Chemistry
• Electrochemistry

Background:

• Transition metal-catalyzed cross-coupling reactions, specifically X-type electrophile cross-coupling (XEC), are vital for C(sp2)-C(sp2) bond formation.
• Achieving selective heterocoupling of two similar electrophiles while suppressing homocoupling remains a significant synthetic challenge.

Purpose of the Study:

• To develop an efficient and selective electrocatalytic approach for heterocoupling similar electrophiles.
• To utilize electricity as a sustainable alternative to traditional redox reagents, minimizing chemical waste.

Main Methods:

• Electrocatalytic synthesis employing controllable applied potential to direct reaction pathways.
• Sequential and controllable electrocatalytic oxidative addition processes.
• Mechanistic investigation using experimental data and Density Functional Theory (DFT) computations.

Main Results:

• Demonstrated a highly selective and general electrocatalytic XEC process for C(sp2)-C(sp2) bond construction.
• Successfully synthesized over 80 diverse compounds, including biaryls, fluorophores, and pharmaceutical intermediates.
• Achieved the first synthesis of solution-processable, low polydispersity conjugated polymers via precise stoichiometric control.

Conclusions:

• The electrocatalytic eXEC method provides a conceptually novel and attractive route for selective C(sp2)-C(sp2) bond formation.
• This approach offers significant advantages in terms of selectivity, generality, and sustainability for synthesizing complex molecules and advanced materials.