Ligand-Enabled “Two-in-One” Metallaphotocatalytic Cross Couplings

ACS Catalysis, Год журнала: 2025, Номер 15(3), С. 1635 - 1654

Опубликована: Янв. 15, 2025

Metallaphotoredox cross coupling (MCC) is ranking among the most advanced synthetic methodology as it can access chemical space that difficult to attain under conventional conditions. Earlier developed MCC mandates an independent transition metal catalyst and respective photocatalyst, thus constituting a dual catalytic manifold. Complementarily, paradigm-shifting metallaphotoredox strategy capitalizes on single photoreactive complex emerging, which brings not only operational simplification but also unexpected mechanistic insights. This perspective compiled recent advances in monocatalytic couplings categorized them based ligands confer distinct photoreactivities various mechanisms. To this end, ligand-enabled oxidative addition, transmetalation, reductive elimination other radical-involving pathways were summarized with notable examples. In way, we wish provide handy guideline for readers who are interested emerging field inspire more future endeavors MCCs beyond.

Язык: Английский

Engineering Atomic Sites and Proton Transfer Microenvironments for Bioinspired Photocatalytic Alcohol‐Amine Coupling

Small, Год журнала: 2025, Номер unknown

Опубликована: Март 21, 2025

Achieving a precise understanding and accurate design of heterogeneous catalysts based on bioinspired principles is challenging yet crucial to digging out optimal materials for artificial catalysis. Here, an ADH-mimicking dual-site photocatalyst (YCuCdS) developed, demonstrates the powerful effects atomic site configuration proton transfer environments alcohol-amine coupling. Mechanism studies reveal that alcohol substrate effectively dehydrogenated at Y sites, forming carbonyl intermediates rapidly experience condensation with amine. Meanwhile, released hydrogen species (Hads) migrate from adjacent Cu sites active S atoms, promoting H2 production hindering over-hydrogenation imine. As result, high imine yield 92% achieved, along rate 7400 µmol g-1 h-1. This work showcases effective strategy bioinspiration.

Язык: Английский

Nickel catalyzed C-N coupling of haloarenes with B2N4 reagents

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Апрель 3, 2025

Язык: Английский