Abstract: Heterogeneous catalysts offer practical advantages for fine chemical manufacturing, including straightforward separation, robustness, and the potential for reuse. Yet, much methodology development in modern organic synthesis still relies on homogeneous catalysts, largely because demanding selective transformations often benefit from well-defined active sites whose local environment can be designed at the molecular level to sustain high activity and selectivity. Single-atom catalysts (SACs)—isolated metal atoms dispersed on a solid support—provide maximal atom utilization and the prospect of more uniform, better-defined active-site structures than conventional nanoparticle catalysts. As a result, SACs are increasingly viewed as a bridge between heterogeneous practicality and molecular-catalyst-like site definition and tunability.[1]
Nitrogen-doped carbon (NDC) is a particularly powerful support for SACs. Acting as a “solid ligand”, NDC can electronically activate and strongly stabilize metal centers through M–N interactions, enabling catalytic behavior that is difficult to achieve on undoped carbon.[2] Here, we present our advances in deploying ZIF-8-derived SACs on NDC for green organic synthesis. Using ZIF-8 as a precursor, pyrolysis affords porous NDC frameworks that anchor atomically dispersed metals and enable highly selective hydrogenation reactions that are challenging for conventional nanoparticle catalysts. Beyond thermocatalysis, we further convert SAC materials into electrodes to access electro-organic synthesis. In particular, a Zn-SAC electrode enables allylation of imines to furnish homoallylic amines with minimal zinc consumption, realizing an electrically driven, “catalytic” organometallic transformation via controlled electroreduction.[3]