The light-driven, nickel-catalyzed cross-electrophile coupling reaction.

Shi Renyi's team at Xi'an Jiaotong University (XJTU) achieved a breakthrough in the field of light-driven, nickel-catalyzed C–C bond construction by synthesizing a recyclable LaFeO₃/LaCoO₃/g-C₃N₄ heterojunction.

Utilizing this material, they realized a highly efficient nickel/photoredox co-catalyzed cross-electrophile coupling reaction between aryl iodides and alkyl halides, eliminating the need for hazardous powder-metal reducing agents.

The research findings, titled Recyclable dual Z-scheme perovskite/g-C₃N₄ heterojunction enables photoredox nickel-catalyzed C(sp²)–C(sp³) cross-electrophile coupling, have been published in the internationally renowned journal Nature Communications.

The construction of carbon-carbon bonds lies at the heart of organic chemistry. Nickel-catalyzed cross-electrophile coupling (XEC) reactions offer a highly efficient and economical synthetic pathway for building C(sp²)–C(sp³) bonds.

Due to its straightforward substrate preparation, excellent functional group tolerance, and low cost, this method has become one of the most promising approaches in contemporary medicinal chemistry and the total synthesis of complex natural products. However, conventional XEC reactions generally rely on stoichiometric amounts of metallic reducing agents, which present several challenges:

a) The use of large quantities of flammable metal powders poses significant safety hazards.

b) The reactions generate environmentally hazardous metal waste (such as MnX₂ and ZnX₂), which is difficult to separate and strictly restricted by waste disposal regulations.

c) The heterogeneous nature of the reaction system leads to poor mixing, which combined with the inconsistent quality of metal reducing agents, easily causes instability in the reaction process.

To address these challenges, the research team developed a recyclable LaFeO₃/LaCoO₃/g-C₃N₄ heterojunction. This heterojunction features a staggered band structure and a dual Z-scheme carrier migration pathway. It enhances photocatalytic performance by synergistically increasing the redox potential and prolonging the lifetime of photogenerated charge carriers through highly efficient interfacial charge transfer.

Utilizing this heterojunction, the team achieved an XEC reaction between aryl iodides and alkyl halides via a dual nickel/photoredox catalytic system, avoiding the use of stoichiometric metal reducing agents. This catalytic system exhibited broad compatibility with various aryl iodides and alkyl halides, delivering target product yields of up to 98 percent.

Furthermore, the perovskite /g-C₃N₄ photocatalyst can be quantitatively recovered and maintains stable activity (yields >90 percent) over five cycles, substantially improving the sustainability of the process. Mechanism studies indicated that the photogenerated electrons from the heterojunction simultaneously mediate both the activation of alkyl halides and the reduction of the nickel catalyst.

This achievement not only realizes the highly efficient construction of C(sp²)–C(sp³) bonds under mild conditions, but also eliminates the safety risks and metal salt pollution associated with traditional metal reducing agents.

This core technology expands the application boundaries of cooperative photoredox/nickel-catalyzed cross-electrophile coupling reactions and promotes the cross-disciplinary integration of heterojunction photocatalysis and organic synthesis.

It provides vital support for the establishment of a sustainable, low-carbon synthetic chemistry framework, holding potential for widespread application in industrial sectors such as pharmaceuticals, agrochemicals, and fine chemicals, contributing to the transition toward greener and lower-carbon development.