Advances in Group VI Metal‐Catalyzed Homogeneous Hydrogenation and Dehydrogenation Reactions DOI Open Access

Tushar Singh,

Vaishnavi Atreya,

Sachin Jalwal

et al.

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(23)

Published: Oct. 10, 2023

Transition metal-catalyzed homogeneous hydrogenation and dehydrogenation reactions for attaining plethora of organic scaffolds have evolved as a key domain research in academia industry. These protocols are atom-economic, greener, line with the goal sustainability, eventually pave way numerous novel environmentally benign methodologies. Appealing progress has been achieved realm catalysis utilizing noble metals. Owing to their high cost, less abundance along toxicity issues led scientific community search sustainable alternatives. In this context, earth- abundant base metals gained substantial attention culminating enormous recent years, predominantly pincer-type complexes nickel, cobalt, iron, manganese. regard, group VI chromium, molybdenum tungsten overlooked remain underdeveloped despite earth-abundance bio-compatibility. This review delineates comprehensive overview arena homogeneously catalysed (de)hydrogenation using molybdenum, till date. Various described; hydrogenation, transfer dehydrogenation, acceptorless dehydrogenative coupling, hydrogen auto transfer, scope brief mechanistic insights.

Language: Английский

Borrowing Hydrogen Amination Reactions: A Complex Analysis of Trends and Correlations of the Various Reaction Parameters DOI
Evgeniya Podyacheva, Oleg I. Afanasyev, Dmitry Vasilyev

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(12), P. 7142 - 7198

Published: June 1, 2022

Borrowing hydrogen or the autotransfer amination is a powerful approach to create single C–N bonds, starting from stable and readily available substrates: amines alcohols. It considered as one of most atom-efficient green methods synthesize complex amines. Herein, we attempted arrange array existing data in comprehensive structured manner determine correlations between experimental conditions catalysis outcome both within different groups catalysts defined using machine analysis. For each type N-nucleophiles (aromatic, aliphatic, heteroaromatic amines, amides), efficient working were suggested, including attributing optimal base temperature regime for metal.

Language: Английский

Citations

83
Recent progress in the synthesis of N-substituted arylamines by reductive cross-coupling of nitroarenes DOI

Jing‐Hao Qin,

Wang Yao,

Jun-Yao Ouyang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(9), P. 2638 - 2664

Published: Jan. 1, 2024

This review describes the recent advances in different reaction types and catalytic systems for construction of C–NAr S–NAr bonds by nitroaromatic reductive cross-coupling.

Language: Английский

Citations

11
Manganese‐Catalyzed Mono‐N‐Methylation of Aliphatic Primary Amines without the Requirement of External High‐Hydrogen Pressure DOI

Jiale Ji,

Yinghao Huo,

Zhaowen Dai

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Feb. 1, 2024

Abstract The synthesis of mono‐ N ‐methylated aliphatic primary amines has traditionally been challenging, requiring noble metal catalysts and high‐pressure H 2 for achieving satisfactory yields selectivity. Herein, we developed an approach the selective coupling methanol amines, without hydrogen, using a manganese‐based catalyst. Remarkably, up to 98 % with broad substrate scope were achieved at low catalyst loadings. Notably, due weak base‐catalyzed alcoholysis formamide intermediates, our novel protocol not only obviates addition but also prevents side secondary ‐methylation, supported by control experiments density functional theory calculations.

Language: Английский

Citations

8
Inducing Cu Charge Redistribution by Modulating Proximity with Zr(OH)4 for Selective Synthesis of Imines and Secondary Amines with Stoichiometric Benzyl Alcohol and Nitrobenzene DOI
Jie Song,

Chunxia Che,

Yiwei Dai

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 1170 - 1181

Published: Jan. 6, 2025

The one-pot synthesis of amines from benzyl alcohol (BA) and nitrobenzene (NB) represents a step-economic method. However, reported works typically require more than 3 equiv BA to complete the transfer hydrogenation NB, few studies can achieve selective imines secondary amines. In our previous work, Zr(OH)4 demonstrated both dehydrogenation capabilities. Building on this, another component Cu was introduced enhance its catalytic performance for catalyzing coupling reaction between stoichiometric NB under H2 atmosphere. physical hybrid catalyst + selectively produced imines, while supported Cu/Zr(OH)4 yielded Characterization mechanism experiments revealed that modulating proximity leads (1) different adsorption abilities N-benzylideneaniline (NBA) (2) interactions in close contact, which stabilized electronic structure forming Cu+/Cu0 ion pairs with strong activation ability. This work presents design strategy offers an approach preparation N-benzylaniline.

Language: Английский

Citations

1
Metal‐Ion/Metal Nanoparticle‐Anchored Porous Organic Polymers as Efficient Catalysts for Organic Transformations – A Recent Overview DOI
Murugavel Kathiresan

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(8)

Published: Feb. 23, 2023

Porous organic polymers are porous materials that interlinked with building blocks by strong covalent bonds. The functional groups on the can be carefully chosen to obtain a POP desired functionalities. In certain cases, pores or voids interact molecules via non-covalent interactions and hence they serve as catalytic centers. many pristine POPs themselves were evaluated heterogeneous catalysts for their activity. inner of act ligand metal ions/metal nanoparticles wide range metal-ion-anchored nanoparticle-loaded reported. These catalyze different reactions metal-based catalysis following pathway. this type catalysis, plays an important role, i. e., it serves carbon matrix, interacts interactions, further in metal/metal-ion-anchored POPs, concentration is highly reduced transformation effectively takes place at interface metal/carbon matrix. Herein, we discuss recent developments metal-ion/metal nanoparticle loaded role various transformations such C-C coupling reactions, borrowing hydrogen CO2 transformations, hydroformylations oxidation alkynes 1,2-diketones C-H arylation reactions.

Language: Английский

Citations

18
Surmounting Alkoxide Trap Strategy: N-Heterocyclic Carbene Chromium(0)-Catalyzed C-Alkylation between Alcohols DOI
Peifeng Su, Zhe Chen,

Jinyu Ni

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(19), P. 12481 - 12493

Published: Sept. 8, 2023

The crucial role of the alkoxide trap problem and impact oxidation state chromium center were demonstrated on catalytic activity due to d-wall issue. Through strategy surmounting trap, a Cr(0) catalyst was presented herein for efficient C-alkylation between alcohols via borrowing hydrogen/hydrogen autotransfer. synthesized bis-(N-heterocyclic carbene)-Cr(0) system shows an performance (40 examples, up 96% yield). Only loading cheap readily available base NaOH is effective enough reaction. Compared with Cr(III)/Cr(II), can well avoid d-p π interaction in key metal-alkoxide intermediate, thus overcoming thermodynamic sink problem. It plausible that Cr(III) systems need be reduced Cr(II) weakening effect enhancing by using reductive strong bases. This should helpful development nonprecious transition metal catalysts.

Language: Английский

Citations

18
Hydrogenation of Esters Catalyzed by Bis(N-Heterocyclic Carbene) Molybdenum Complexes DOI Creative Commons
Niklas F. Both, Jannik Thaens,

Anke Spannenberg

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4082 - 4092

Published: March 1, 2024

A series of Mo complexes bearing inexpensive bidentate bis(NHC) ligands have been synthesized and characterized by NMR IR spectroscopy as well single crystal XRD analysis. These proved to be efficient for the catalytic hydrogenation aliphatic aromatic esters (>35 examples) operating at low catalyst loadings (0.5–2 mol %) temperatures (80–120 °C). Various functional groups, e.g., C═C double bonds, nitriles, alcohols, tertiary amines, halides, acetals, heteroaromatic substrates, lactones, diesters, are tolerated optimal system. Based on spectroscopic investigations, control experiments DFT computations a non-bifunctional outer-sphere mechanism is proposed.

Language: Английский

Citations

8
Metal-acid synergistic catalysis accelerates the hydrogen borrowing amination of alcohols by confining Ru sites in Beta zeolite DOI
Yue Wu, Cailing Chen, Zhuo Xiong

et al.

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 493, P. 152457 - 152457

Published: May 24, 2024

Language: Английский

Citations

6
Half-Sandwich Iridium Complexes with Hydrazone Ligands: Synthesis and Catalytic Activity in N-Alkylation of Anilines or Nitroarenes with Alcohols via Hydrogen Autotransfer DOI
Yang Wang,

Fang-Lei Zhang,

Zhenjiang Liu

et al.

Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 61(27), P. 10310 - 10320

Published: June 29, 2022

Here, we synthesize a series of hydrazone-based N,O-chelate half-sandwich iridium complexes through facile route. All air-stable show high catalytic activity in N-alkylation broad scope aniline derivatives and alcohols with liberating water as the sole byproduct. This reaction provides smooth route to diverse monoalkylated amines good excellent yields at moderate temperature low catalyst loading. Moreover, challenging process using nitroarene substrates coupling partners is also carried out this system. The mechanistic study shows that present catalysis proceeds hydrogen borrowing mechanism. iridium(III) 1-4 are characterized by infrared (IR) spectroscopy, nuclear magnetic resonance (NMR) elemental analysis.

Language: Английский

Citations

23
N, S Co-Coordinated Zinc Single-Atom Catalysts for N-Alkylation of Aromatic Amines with Alcohols: The Role of S-Doping in the Reaction DOI Creative Commons
Xueping Zhang, Qiang Zhang,

Jiacheng Reng

et al.

Nanomaterials, Journal Year: 2023, Volume and Issue: 13(3), P. 445 - 445

Published: Jan. 21, 2023

S-doping emerged as a promising approach to further improve the catalytic performance of carbon-based materials for organic synthesis. Herein, facile and gram-scale strategy was developed using zeolitic imidazole frameworks (ZIFs) precursor fabrication ZIF-derived N, S co-doped carbon-supported zinc single-atom catalyst (CNS@Zn1-AA) via pyrolysis S-doped ZIF-8, which modified by aniline, ammonia thiourea prepared one-pot ball milling at room temperature. This catalyst, in Zn is dispersed single atom, displays superior activity N-alkylation hydrogen-borrowing (120 °C, turnover frequency (TOF) up 8.4 h−1). significantly enhanced CNS@Zn1-AA, it increased specific surface area defects this material simultaneously electron density sites catalyst. Furthermore, had excellent stability recyclability, no obvious loss after eight runs.

Language: Английский

Citations

12