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

Single‐Atom Catalysis in Organic Synthesis DOI Creative Commons
Vitthal B. Saptal, Vincenzo Ruta, Mark A. Bajada

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: March 15, 2023

Single-atom catalysts hold the potential to significantly impact chemical sector, pushing boundaries of catalysis in new, uncharted directions. These materials, featuring isolated metal species ligated on solid supports, can exist many coordination environments, all which have shown important functions specific transformations. Their emergence has also provided exciting opportunities for mimicking metalloenzymes and bridging gap between homogeneous heterogeneous catalysis. This Review outlines impressive progress made recent years regarding use single-atom organic synthesis. We illustrate knowledge gaps search more sustainable, earth-abundant synthetic applications.

Language: Английский

Citations

115
Sustainable Aerobic Allylic C–H Bond Oxidation with Heterogeneous Iron Catalyst DOI
Yijie Jiang,

Sanxia Chen,

Y. -C. Chen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2769 - 2778

Published: Jan. 19, 2024

Emerging techniques are revolutionizing the realm of chemical synthesis by introducing new avenues for C–H bond functionalization, which have been exploited pharmaceuticals, natural compounds, and functional materials. Allylic oxidation alkenes serves as possibly most employed functionalization reaction. However, sustainable selective approaches remain scarce, majority existing conditions still hinge on hazardous oxidants or costly metal catalysts. In this context, we introduce a heterogeneous iron catalyst that addresses above-mentioned concerns showcasing aerobic steroids, terpenes, simple olefins to corresponding enone products. This novel method provides powerful tool arsenal allylic while minimizing environmental concerns.

Language: Английский

Citations

21
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

7
Recent advances in the accessibility, synthetic utility, and biological applications of aziridines DOI Creative Commons
Christian Dank, Laura Ielo

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(22), P. 4553 - 4573

Published: Jan. 1, 2023

Compounds featuring aziridine moieties are widely known and extensively reported in the literature. Due to their great potential from both synthetic pharmacological points of view, many researchers have focused efforts on development new methodologies for preparation transformation these interesting compounds. Over years, more ways obtain molecules bearing three-membered functional groups, which challenging due inherent reactivity, been described. Among them, several sustainable. In this review, we report recent advances biological chemical evolution derivatives, particular, variety described synthesis aziridines transformations leading formation such as 4-7 membered heterocycles pharmaceutical interest promising activities.

Language: Английский

Citations

39
Reductive Coupling of Nitroarenes and HCHO for General Synthesis of Functional Ethane-1,2-diamines by a Cobalt Single-Atom Catalyst DOI
Jialu Sun, Huanfeng Jiang, Pierre H. Dixneuf

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(31), P. 17329 - 17336

Published: July 7, 2023

Despite the extensive applications, selective and diverse access to N,N'-diarylethane-1,2-diamines remains, date, a challenge. Here, by developing bifunctional cobalt single-atom catalyst (CoSA-N/NC), we present general method for direct synthesis of such compounds via reductive coupling cheap abundant nitroarenes formaldehyde, featuring good substrate functionality compatibility, an easily accessible base metal with excellent reusability, high step atom efficiency. Mechanistic studies reveal that N-anchored single atoms (CoN4) serve as catalytically active sites reduction processes, N-doped carbon support enriches HCHO timely trap in situ formed hydroxyamines affords requisite nitrones under weak alkaline conditions, subsequent inverse electron demand 1,3-dipolar cycloaddition imines followed hydrodeoxygenation cycloadducts furnishes products. In this work, concept catalyst-controlled nitroarene create specific building blocks is anticipated develop more useful chemical transformations.

Language: Английский

Citations

39
Well‐defined N3C1‐anchored Single‐Metal‐Sites for Oxygen Reduction Reaction DOI
Senhe Huang, Diana Tranca, F. Rodríguez-Hernández

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 23, 2023

N-, C-, O-, S-coordinated single-metal-sites (SMSs) have garnered significant attention due to the potential for significantly enhanced catalytic capabilities resulting from charge redistribution. However, challenges persist in precise design of well-defined such SMSs, and fundamental comprehension has long been impeded case-by-case reports using carbon materials as investigation targets. In this work, molecular catalysts with N3 C1 -anchored i.e., N-confused metalloporphyrins (NCPor-Ms), are calculated their oxygen reduction activity. Then, NCPor-Ms corresponding N4 SMSs (metalloporphyrins, Por-Ms), synthesized activity evaluation. Among all, NCPor-Co reaches top established volcano plots. also shows highest half-wave 0.83 V vs. RHE, which is much better than that Por-Co (0.77 RHE). Electron-rich, low band gap regulated d-band center contribute high NCPor-Co. This study delves into examination asymmetric SMS catalysts, encompassing both theoretical experimental facets. It serves a pioneering step towards enhancing facilitating development high-performance catalysts.

Language: Английский

Citations

24
Cobalt-Catalyzed Acceptorless Dehydrogenation of Primary Amines to Nitriles DOI

Haitao Tian,

Cai‐Yun Ding,

Rong‐Zhen Liao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(17), P. 11801 - 11810

Published: April 16, 2024

The direct double dehydrogenation from primary amines to nitriles without an oxidant or hydrogen acceptor is both intriguing and challenging. In this paper, we describe a non-noble metal catalyst capable of realizing such transformation with high efficiency. A cobalt-centered N,N-bidentate complex was designed employed as metal–ligand cooperative catalyst. Detailed kinetic studies, control experiments, DFT calculations revealed the crucial hydride transfer, proton evolution processes. Finally, tandem outer-sphere/inner-sphere mechanism proposed for through imine intermediate.

Language: Английский

Citations

15
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
Heterogeneous Iridium-Catalyzed Carbene N–H Bond Insertion with α-Alkyl Diazo Esters DOI

Ping Guo,

Yan Chen, Tao Lei

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4690 - 4698

Published: March 13, 2024

A heterogeneous iridium single-atom site catalyst (Ir-SA) was synthesized and investigated in catalyzing the carbene insertion reaction with challenging α-alkyl diazo ester substrates. With only 0.23 mol % loading, our Ir-SA demonstrated remarkable performance N–H bond reactions involving various (hetero) aryl amines coupled esters. Notably, case of using a chiral diamino substrate two reactive sites, exhibited high selectivity toward single insertion, leading to generation class unsymmetric ligands. Further mechanism study revealed that lower activation barrier associated step, as compared either β-hydride elimination or downstream dual accounted for observed this catalyzed by Ir-SA.

Language: Английский

Citations

10
Advancing Heterogeneous Organic Synthesis With Coordination Chemistry‐Empowered Single‐Atom Catalysts DOI

Bo‐Chao Ye,

Wenhao Li, Xia Zhang

et al.

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

Published: Sept. 18, 2024

Abstract For traditional metal complexes, intricate chemistry is required to acquire appropriate ligands for controlling the electron and steric hindrance of active centers. Comparatively, preparation single‐atom catalysts much easier with more straightforward effective accesses arrangement control The presence coordination atoms or neighboring functional on supports' surface ensures stability single‐atoms their interactions individual substantially regulate performance Therefore, collaborative interaction between surrounding environment enhances initiation reaction substrates formation transformation crucial intermediate compounds, which imparts significant catalytic efficacy, rendering them a valuable framework investigating correlation structure activity, as well mechanism in organic reactions. Herein, comprehensive overviews both homogeneous complexes reactions are provided. Additionally, reflective conjectures about advancement synthesis also proposed present reference later development.

Language: Английский

Citations

10