Visible-Light-Driven Catalytic Dehalogenation of Trichloroacetic Acid and α-Halocarbonyl Compounds: Multiple Roles of Copper DOI Creative Commons

Abigail J. Thillman,

Erin C. Kill,

Alexander N. Erickson

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(5), P. 3873 - 3881

Published: Feb. 19, 2025

Herein, we report the reaction development and mechanistic studies of visible-light-driven Cu-catalyzed dechlorination trichloroacetic acid for highly selective formation monochloroacetic acid. Visible-light-driven transition metal catalysis via an inner-sphere pathway features dual roles species in photoexcitation substrate activation steps, a detailed understanding their is crucial further light-driven catalysis. This catalytic method, which environmentally desired ascorbic as hydrogen atom source water/ethanol solvent, can be applied to dehalogenation variety halocarboxylic acids amides. Spectroscopic, X-ray crystallographic, kinetic have revealed mechanism copper photoexcitation, thermal first C–Cl bond, excited-state second bond chlorine transfer.

Language: Английский

Ligand-Enabled “Two-in-One” Metallaphotocatalytic Cross Couplings DOI
Jianbin Li, Ding Zhang, Zheng Hu

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1635 - 1654

Published: Jan. 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.

Language: Английский

Citations

3
Visible-Light-Driven Catalytic Dehalogenation of Trichloroacetic Acid and α-Halocarbonyl Compounds: Multiple Roles of Copper DOI Creative Commons

Abigail J. Thillman,

Erin C. Kill,

Alexander N. Erickson

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(5), P. 3873 - 3881

Published: Feb. 19, 2025

Herein, we report the reaction development and mechanistic studies of visible-light-driven Cu-catalyzed dechlorination trichloroacetic acid for highly selective formation monochloroacetic acid. Visible-light-driven transition metal catalysis via an inner-sphere pathway features dual roles species in photoexcitation substrate activation steps, a detailed understanding their is crucial further light-driven catalysis. This catalytic method, which environmentally desired ascorbic as hydrogen atom source water/ethanol solvent, can be applied to dehalogenation variety halocarboxylic acids amides. Spectroscopic, X-ray crystallographic, kinetic have revealed mechanism copper photoexcitation, thermal first C–Cl bond, excited-state second bond chlorine transfer.

Language: Английский

Citations

0