Radical Reactions in Organic Synthesis: Exploring in-, on-, and with-Water Methods DOI Creative Commons
Chryssostomos Chatgilialoglu, Sebastián Barata‐Vallejo, Thanasis Gimisis

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(3), P. 569 - 569

Published: Jan. 23, 2024

Radical reactions in water or aqueous media are important for organic synthesis, realizing high-yielding processes under non-toxic and environmentally friendly conditions. This overview includes (i) a general introduction to chemistry media, (ii) synthetic approaches in, on, with as well heterogeneous phases, (iii) of carbon-centered radicals (or deuterium oxide) activated through coordination various Lewis acids, (iv) photocatalysis (v) applications bioinspired by naturally occurring processes. A wide range chemical strategies different experimental conditions have been reviewed that lead functional group translocation transformation reactions, leading the preparation complex molecules. These results reveal how solvent/medium/reagent radical has matured over last two decades, further discoveries anticipated near future.

Language: Английский

Organo‐Mediator Enabled Electrochemical Deuteration of Styrenes DOI

Keming Yang,

Tian Feng, Youai Qiu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 12, 2023

Despite widespread use of the deuterium isotope effect, selective labeling chemical molecules remains a major challenge. Herein, facile and general electrochemically driven, organic mediator enabled deuteration styrenes with oxide (D2 O) as economical source was reported. Importantly, this transformation could be suitable for various electron rich mediated by triphenylphosphine (TPP). The reaction proceeded under mild conditions without transition-metal catalysts, affording desired products in good yields excellent D-incorporation (D-inc, up to >99 %). Mechanistic investigations means experiments cyclic voltammetry tests provided sufficient support transformation. Notably, method proved powerful tool late-stage biorelevant compounds.

Language: Английский

Citations

48
Keto-anthraquinone covalent organic framework for H2O2 photosynthesis with oxygen and alkaline water DOI Creative Commons

Xiangcheng Zhang,

Silian Cheng,

Chao Chen

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 26, 2024

Hydrogen peroxide photosynthesis suffers from insufficient catalytic activity due to the high energy barrier of hydrogen extraction H2O. Herein, we report that mechanochemically synthesized keto-form anthraquinone covalent organic framework which is able directly synthesize H2O2 (4784 μmol h-1 g-1 at λ > 400 nm) oxygen and alkaline water (pH = 13) in absence any sacrificial reagents. The strong alkalinity resulted formation OH-(H2O)n clusters water, were adsorbed on keto moieties within then dissociated into O2 active hydrogen, because was largely lowered. produced reacted with generate anthrahydroquinone, subsequently oxidized by produce H2O2. This study ultimately sheds light importance H2O for demonstrates synthesis achievable under conditions.

Language: Английский

Citations

46
Atomically dispersed low-valent Au boosts photocatalytic hydroxyl radical production DOI
Zhenyuan Teng, Hongbin Yang, Qitao Zhang

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(8), P. 1250 - 1260

Published: June 25, 2024

Language: Английский

Citations

37
Fe-N co-doped carbon nanofibers with Fe3C decoration for water activation induced oxygen reduction reaction DOI Creative Commons
Shaoxiong Li,

Gengyu Xing,

Sheng Zhao

et al.

National Science Review, Journal Year: 2024, Volume and Issue: 11(10)

Published: June 3, 2024

Proton activity at the electrified interface is central to kinetics of proton-coupled electron transfer (PCET) reactions in electrocatalytic oxygen reduction reaction (ORR). Here, we construct an efficient Fe

Language: Английский

Citations

27
Electroreduction of unactivated alkenes using water as hydrogen source DOI Creative Commons
Yanwei Wang, Qian Wang, Lei Wu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 30, 2024

Abstract Herein, we report an electroreduction of unactivated alkyl alkenes enabled by [Fe]-H, which is provided through the combination anodic iron salts and silane generated in situ via cathodic reduction, using H 2 O as H-source. The catalytic amounts Si-additive work H-carrier from to generate a highly active species under continuous electrochemical conditions. This approach shows broad substrate scope good functional group compatibility. In addition hydrogenation, use D instead provides desired deuterated products yields with excellent D-incorporation (up >99%). Further late-stage hydrogenation complex molecules drug derivatives demonstrate potential application pharmaceutical industry. Mechanistic studies are performed provide support for proposed mechanistic pathway.

Language: Английский

Citations

21
Recent advances for enhanced photodynamic therapy: from new mechanisms to innovative strategies DOI Creative Commons

Xia Wang,

Jinlei Peng,

Chi Meng

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(31), P. 12234 - 12257

Published: Jan. 1, 2024

Photodynamic therapy (PDT) has been developed as a potential cancer treatment approach owing to its non-invasiveness, spatiotemporal control and limited side effects. Currently, great efforts have made improve the PDT effect in terms of safety efficiency. In this review, we highlight recent advances innovative strategies for enhanced PDT, including (1) development novel radicals, (2) design activatable photosensitizers based on TME light, (3) photocatalytic NADH oxidation damage mitochondrial electron transport chain. Additionally, new mechanisms are also presented an inspiration PSs. Finally, discuss current challenges future prospects clinical practice these strategies. It is hoped that review will provide angle understanding relationship between intratumoural redox environment mechanisms, ideas smart systems.

Language: Английский

Citations

17
Rationally designed photothermal-pyroelectric Fe0.9Ni0.1S2/ZnSnO3 Z-scheme heterojunction for promoting electrical charge polarization towards optimized photocatalytic H2 evolution and intermolecular N-N coupling reaction DOI
Zuming He, Yongmei Xia,

Fahui Wang

et al.

Separation and Purification Technology, Journal Year: 2024, Volume and Issue: unknown, P. 130201 - 130201

Published: Oct. 1, 2024

Language: Английский

Citations

17
Recent research progress of MOFs-Based heterostructures for photocatalytic hydrogen evolution DOI
Jiaming Li, Jia Jia, Deping Wang

et al.

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 498, P. 155194 - 155194

Published: Aug. 26, 2024

Language: Английский

Citations

16
Diatomic Palladium Catalyst for Enhanced Photocatalytic Water-Donating Transfer Hydrogenation DOI
En Zhao, Jordi Morales‐Vidal, Yue Yang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 5, 2025

Diatomic catalysts (DACs) present unique opportunities for harnessing ensemble effects between adjacent metal atoms, thus, expanding the properties of single-atom (SACs). However, precise preparation and characterization this type catalyst remains challenging. Following a precursor-preselected strategy, here, we report synthesis carbon nitride-supported Pd-DAC, which achieves an excellent yield 92% photocatalytic water-donating transfer hydrogenation 4-vinylphenol to 4-ethylphenol, far exceeding that other species, including Pd single atoms (47%) nanoparticles (1%). Combining transmission electron microscopy with standardized machine learning atom-detection methods confirms stabilization substantial fraction dimeric species over nitride. Density functional theory (DFT) simulations associate outstanding performance Pd-DAC enhanced substrate activation in path compared Pd-SAC. The work provides criteria DACs demonstrates application is sustainable eco-friendly conventional technologies.

Language: Английский

Citations

4
Unveiling the Contribution of Hydrogen Radicals to Per- and Polyfluoroalkyl Substances (PFASs) Defluorination: Applicability and Degradation Mechanisms DOI
Yuwen Qi,

Yinbo Yang,

Xue Yu

et al.

Environmental Science & Technology, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 12, 2025

At present, the defluorination of per- and polyfluoroalkyl substances (PFASs), including perfluoroether compounds as substitutes perfluorooctanoic acid (PFOA) perfluorooctanesulfonate, is limited by effective active species produced during oxidation-reduction process. The contribution hydrogen radical (•H) a companion substance in photoreduction electrocatalytic degradation PFASs has been neglected. Herein, we demonstrate that perfluorocarboxylic acids such PFOA hexafluoropropylene oxide dimer (GenX) underwent near-complete photodegradation continuously generating •H through perfluoroalkyl activation water under UV irradiation without any reagents catalysts. Importantly, initial dissolved oxygen, H+, impurities surface scarcely inhibited PFASs. difference mechanism between GenX action was elucidated combining theoretical calculations with targeted nontargeted analysis methods. investigation different indicates were not easily photodegraded via reduction compared other compounds, whereas polyfluorinated which some F atoms replaced Cl more prone to elimination. However, UV/•H system ineffective against perfluorosulfonic acids. This study provides an unprecedented perspective for further development removal technology design alternative are easy eliminate.

Language: Английский

Citations

3