Biomass‐Derived Cu‐Catalyzed General C—X (X = C, N, O) Bond Formation: Carbenoid Insertion Reactions of C—H, N—H, O—H Bond and Late‐stage Functionalization of Drug Molecules† DOI Open Access

Fu‐Hua Qin,

Wenxuan Xue, Conghui Tang

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 7, 2025

Comprehensive Summary The development of sustainable and efficient catalytic systems for the formation C—C, C—N, C—O bonds is a fundamental goal in modern synthetic chemistry. We present biomass‐derived Cu/Chitosan‐800 catalyst that facilitates range carbenoid insertion reactions into C—H, N—H, O—H bonds. This demonstrates remarkable activity, enabling functionalization diverse substrates, including late‐stage modification drug molecules with up to 95% yield good recyclability. Our findings highlight catalyst's potential advancing environmentally friendly chemical transformations, offering promising tool pharmaceutical synthesis organic synthesis.

Language: Английский

Multifunctional carbon nitride nanoarchitectures for catalysis DOI
Prashant Kumar, Gurwinder Singh, Xinwei Guan

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(21), P. 7602 - 7664

Published: Jan. 1, 2023

Carbon nitrides, with feasibility of tailored band gap via suitable nanoarchitectonics, are deemed as best catalysts amongst existing materials, especially for HER, OWS, COR, NRR, water oxidation, pollutant removal, and organocatalysis.

Language: Английский

Citations

101
Modeling Single‐Atom Catalysis DOI Creative Commons
Giovanni Di Liberto, Gianfranco Pacchioni

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(46)

Published: Sept. 25, 2023

Electronic structure calculations represent an essential complement of experiments to characterize single-atom catalysts (SACs), consisting isolated metal atoms stabilized on a support, but also predict new catalysts. However, simulating SACs with quantum chemistry approaches is not as simple often assumed. In this work, the factors that reliable simulation activity are examined. The Perspective focuses importance precise atomistic characterization active site, since even small changes in atom's surroundings can result large reactivity. dynamical behavior and stability under working conditions, well adopting appropriate methods solve Schrödinger equation for quantitative evaluation reaction energies addressed. relevance model adopted. For electrocatalysis must include effects solvent, presence electrolytes, pH, external potential. Finally, it discussed how similarities between coordination compounds may intermediates usually observed electrodes. When these aspects adequately considered, predictive power electronic quite limited.

Language: Английский

Citations

56
Single‐Atom Iron Catalyst as an Advanced Redox Mediator for Anodic Oxidation of Organic Electrosynthesis DOI

Xin‐Yu Wang,

Yong‐Zhou Pan,

Jiarui Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(27)

Published: April 23, 2024

Homogeneous electrocatalysts can indirect oxidate the high overpotential substrates through single-electron transfer on electrode surface, enabling efficient operation of organic electrosynthesis catalytic cycles. However, problems this chemistry still exist such as dosage, difficult recovery, and low efficiency. Single-atom catalysts (SACs) exhibit atom utilization excellent activity, hold great promise in addressing limitations homogeneous catalysts. In view this, we have employed Fe-SA@NC an advanced redox mediator to try change situation. was synthesized using encapsulation-pyrolysis method, it demonstrated remarkable performance a range reported reactions, construction various C-C/C-X bonds. Moreover, potential exploring new synthetic method for electrosynthesis. We develop electro-oxidative ring-opening transformation cyclopropyl amides. reaction system, showed good tolerance drug molecules with complex structures, well flow electrochemical syntheses gram-scale transformations. This work highlights SACs electrosynthesis, thereby opening avenue chemistry.

Language: Английский

Citations

30
Fabricating a Structured Single‐Atom Catalyst via High‐Resolution Photopolymerization 3D Printing DOI Creative Commons

Jiachengjun Luo,

Vincenzo Ruta, Ik Seon Kwon

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: April 29, 2024

Abstract This study introduces a novel solution to the design of structured catalysts, integrating single‐piece 3D printing with single‐atom catalysis. Structured catalysts are widely employed in industrial processes, as they provide optimal mass and heat transfer, leading more efficient use catalytic materials. They conventionally prepared using ceramic or metallic bodies, which then washcoated impregnated catalytically active layers. However, this approach may lead adhesion issues latter. By employing photopolymerization printing, stable catalyst is directly shaped into stand‐alone, material. The battery characterization methods present confirms uniform distribution species structural integrity Computational fluid dynamics simulations applied demonstrate enhanced momentum transfer light within body. materials finally evaluated continuous‐flow photocatalytic oxidation benzyl alcohol benzaldehyde, relevant reaction prepare biomass‐derived building blocks. innovative reported herein manufacture circumvents complexities traditional synthetic methods, offering scalability efficiency improvements, highlights transformative role catalysis engineering revolutionize catalysts’ design.

Language: Английский

Citations

20
Resolving the Nanostructure of Carbon Nitride‐Supported Single‐Atom Catalysts DOI Creative Commons
Nicolò Allasia, Shuai Xu,

Sadaf Fatima Jafri

et al.

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

Abstract Single‐atom catalysts (SACs) are gathering significant attention in chemistry due to their unique properties, offering uniform active site distribution and enhanced selectivity. However, precise structure often remains unclear, with multiple models proposed the literature. Understanding coordination environment of at atomic level is crucial for explaining catalytic activity. Here, a comprehensive study SACs made carbon nitride (CN x ) containing isolated nickel atoms presented. Using combination synthesis techniques characterization methods including Fourier‐transform infrared spectroscopy, X‐ray absorption spectroscopy (XAS), density functional theory (DFT) calculations, local centers CN ‐supported investigated. These results challenge conventional structural propose new architecture that better aligns current experimental evidence. This serves as foundational step toward rational approach catalyst development can facilitate more design application these innovative catalysts.

Language: Английский

Citations

9
Enhanced Three-Component Chloro-/Azido-Fluoroalkylation of Unactivated Alkenes via the Proximity Effect in a Heterogenous Metallaphotocatalyst DOI
Xiaolin Shi, Maolin Li,

Yuanjun Zhao

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 2180 - 2191

Published: Jan. 22, 2025

Heterogeneous metallaphotocatalytic chemical transformations employing a recyclable catalyst are highly desirable for organic synthesis. However, the rational design and controlled preparation of well-defined, site-isolated metal/photo bifunctional heterogeneous catalysts to achieve this goal remain significant challenge. In study, we demonstrate covalent attachment homogeneous molecular MnSalen complex (where Salen = N,N′-bis(salicylidene)ethylenediamine) onto surface graphitic carbon nitride (CN) via an amide bond visible-light-driven chloro- azido-fluoroalkylation unactivated alkenes. The linkage between CN not only facilitates electron delocalization enhances light-harvesting capabilities photosensitizer but also exerts proximity effect that markedly ability Mn sites capture alkyl radical intermediates during reaction process. A diverse set alkenes could be efficiently azido-fluoroalkylated their corresponding difunctionalized products in moderate high yields with good functional group compatibility. Furthermore, practicability protocol is illustrated through late-stage diversification various bioactive compounds pharmaceuticals. Notably, integrated photocatalyst demonstrates stability can recycled at least 10 times without loss activity selectivity.

Language: Английский

Citations

3
Integrative catalytic pairs for efficient multi-intermediate catalysis DOI
Qilun Wang, Yaqi Cheng, Hong Bin Yang

et al.

Nature Nanotechnology, Journal Year: 2024, Volume and Issue: 19(10), P. 1442 - 1451

Published: Aug. 5, 2024

Language: Английский

Citations

17
Single-Atom Fe-Catalyzed Acceptorless Dehydrogenative Coupling to Quinolines DOI

Yanze Lu,

Zhu Meiling,

Sanxia Chen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(33), P. 23338 - 23347

Published: Aug. 6, 2024

A single-atom iron catalyst was found to exhibit exceptional reactivity in acceptorless dehydrogenative coupling for quinoline synthesis, outperforming known homogeneous and nanocatalyst systems. Detailed characterizations, including aberration-corrected HAADF-STEM, XANES, EXAFS, jointly confirmed the presence of atomically dispersed centers. Various functionalized quinolines were efficiently synthesized from different amino alcohols a range ketones or alcohols. The achieved turnover number (TON) up 10

Language: Английский

Citations

13
Hidden Impurities Generate False Positives in Single Atom Catalyst Imaging DOI Creative Commons
Nicolò Allasia, Sean M. Collins, Quentin M. Ramasse

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: May 15, 2024

Single-atom catalysts (SACs) are an emerging class of materials, leveraging maximum atom utilization and distinctive structural electronic properties to bridge heterogeneous homogeneous catalysis. Direct imaging methods, such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, commonly applied confirm the atomic dispersion active sites. However, interpretations data from these techniques can be challenging due simultaneous contributions intensity impurities introduced during synthesis processes, well any variation in position relative focal plane beam. To address this matter, paper presents a comprehensive study on two representative SACs containing isolated nickel or copper atoms. Spectroscopic techniques, including X-ray absorption spectroscopy, were employed prove high metal catalytic Employing microscopy combined with single-atom-sensitive energy loss we scrutinized thin specimens provide unambiguous chemical identification observed single-atom species thereby distinguish sites at level. Overall, underscores complexity characterization establishes importance use spectroscopy tandem resolution fully reliably characterize catalysts.

Language: Английский

Citations

12
A Guide to Chemical Reactions Design in Carbon Nitride Photocatalysis DOI
Aleksandr Savateev,

Jingru Zhuang

ChemPhotoChem, Journal Year: 2024, Volume and Issue: 8(4)

Published: Jan. 5, 2024

Abstract Graphitic carbon nitride semiconductors are inexpensive and reusable photocatalysts, which actively studied in organic synthesis. Successful design of photocatalytic reactions is based on the next considerations. i) Thermodynamic feasibility photoinduced processes, involve transfer electrons or electron‐proton couples. ii) Redox activity reagents. iii) Reactivity open‐shell intermediates generated from Herein, we summarize current understanding how local chemical structure graphitic nitrides their redox potentials used to reactions. This work intends serve as a guideline for materials scientists, who willing apply involving substrates, chemists, interested dive into heterogeneous photocatalysis.

Language: Английский

Citations

10