Borrowing Hydrogen Amination Reactions: A Complex Analysis of Trends and Correlations of the Various Reaction Parameters

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

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Chemistry of Compounds Based on 1,2,3-Triazolylidene-Type Mesoionic Carbenes

JACS Au, Journal Year: 2021, Volume and Issue: 2(1), P. 22 - 57

Published: Dec. 15, 2021

Mesoionic carbenes (MICs) of the 1,2,3-triazolylidene type have established themselves as a popular class compounds over past decade. Primary reasons for this popularity are their modular synthesis and strong donor properties. While such MICs mostly been used in combination with transition metals, few years also seen utility together main group elements. In paper, we present an overview recent developments on that include, among others, (i) cationic anionic MIC ligands, (ii) donor/acceptor properties these ligands focus several methods known estimating properties, (iii) detailed 3d metal complexes (iv) results redox photophysical based (v) electrocatalysis, redox-switchable catalysis, small-molecule activation to highlight applications contemporary chemistry. By discussing aspects from synthetic, spectroscopic, application point view classes compounds, state art containing perspective future research field.

Language: Английский

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Multi-Functionality of Methanol in Sustainable Catalysis: Beyond Methanol Economy

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(22), P. 15013 - 15053

Published: Nov. 6, 2023

Methanol is a fundamental feedstock and widely used in the chemical petroleum industries. It can serve as C1 source to make variety of C–C C–N bond formation dehydrogenative coupling products, which have important applications natural products drug discovery. A high hydrogen content (12.5 wt%) methanol makes it an effective H2 donor for transfer hydrogenation various reducible functional groups. plethora transition metal-based processes been developed using methanol. Notably, recent review articles focused on aspect However, more updated that examines challenges both C1-source H2-source organic transformations contributing concept economy has not presented yet. This Review summarizes (homogeneous, heterogeneous, photo-) catalyst system C-, N-, O-methylation ketones, alcohols, amides, nitriles, heterocyclic compounds, sulfones, amines, sulfonamides direct N-methylation nitro compounds under borrowing strategy N-formylation amines acceptorless dehydrogenation source. also covers insights into reaction mechanisms role carefully selected ligands metal catalysis activation incorporation -CD3, methylation molecules. Moreover, describes groups such aldehydes, alkynes, with detail.

Language: Английский

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Borrowing Hydrogen and Acceptorless Dehydrogenative Coupling in the Multicomponent Synthesis of N‐Heterocycles: A Comparison between Base and Noble Metal Catalysis

European Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 2021(46), P. 6206 - 6223

Published: Nov. 4, 2021

Abstract Acceptorless dehydrogenative coupling reactions (ADC) and hydrogen transfer strategies (HT) provide a powerful tool in the multicomponent formation of N ‐ heterocycles. A broad variety complex products can be obtained starting from simple, cheap commercially available reagents. The protocols are highly atom‐efficient, as water, dihydrogen, or some cases peroxide, only by‐products. Moreover, neither further reducing oxidizing agents, nor external general required. Especially base metal‐catalyzed become ever more important. Therefore, recent years, various different manganese, iron, cobalt, nickel copper catalysts have been developed. This Minireview highlights progress that has made by using abundant metal complexes to promote cyclizations for heterocycles compares their performance with noble catalyst systems.

Language: Английский

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Recent advances in sustainable organic transformations using methanol: expanding the scope of hydrogen-borrowing catalysis

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(24), P. 7077 - 7096

Published: Jan. 1, 2021

Recent progress relating to sustainable approaches using methanol as a C1-alkylating agent for C–Me and N–Me bond formation is discussed.

Language: Английский

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Dehydrogenative Synthesis of Quinolines and Quinazolines via Ligand-Free Cobalt-Catalyzed Cyclization of 2-Aminoaryl Alcohols with Ketones or Nitriles

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(19), P. 12596 - 12607

Published: Sept. 26, 2022

We present a convenient and efficient protocol to synthesize quinolines quinazolines in one pot under mild conditions. A variety of substituted were synthesized good excellent yields (up 97% yield) from the dehydrogenative cyclizations 2-aminoaryl alcohols ketones catalyzed by readily available Co(OAc)2·4H2O. This cobalt catalytic system also showed high activity reactions 2-aminobenzyl with nitriles, affording various quinazoline derivatives 95% yield). The offers an environmentally benign approach for synthesis N-heterocycles employing earth-abundant salt ligand-free

Language: Английский

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Ruthenium pincer complex catalyzed efficient synthesis of quinoline, 2-styrylquinoline and quinazoline derivatives via acceptorless dehydrogenative coupling reactions

Catalysis Science & Technology, Journal Year: 2022, Volume and Issue: 12(18), P. 5695 - 5702

Published: Jan. 1, 2022

The synthesis of N-heterocycles has been considered an emerging area chemical research due to their extensive utilization in pharmaceuticals, materials science, and natural product synthesis.

Language: Английский

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Recent advances in the catalytic N-methylation and N-trideuteromethylation reactions using methanol and deuterated methanol

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 474, P. 214827 - 214827

Published: Oct. 11, 2022

Language: Английский

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Synthesis of Polyethyleneimines from the Manganese‐Catalysed Coupling of Ethylene Glycol and Ethylenediamine

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(29)

Published: May 17, 2023

Polyethyleneimines find many applications in products such as detergents, adhesives, cosmetics, and for processes tissue culture, gene therapy, CO

Language: Английский

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Amine Functionalized Pincer-like Azo-aromatic Complexes of Cobalt and Their Catalytic Activities in the Synthesis of Quinoline via Acceptorless Dehydrogenation of Alcohols

Organometallics, Journal Year: 2023, Volume and Issue: 42(15), P. 1854 - 1868

Published: July 6, 2023

Herein we disclose a series of phosphine-free cobalt(II)-based catalytic systems bearing redox non-innocent amine functionalized azo-aromatic pincer-like ligand for the synthesis quinoline by dehydrogenative oxidation 2-amino benzyl alcohol and subsequent coupling with ketone. All precatalysts were characterized thoroughly using various spectroscopic techniques DFT studies. The protocol was efficient versatile, providing major advances in quinoline. It also found to be applicable gram-scale quinolines as well. Several control experiments, kinetic studies, studies have proposed plausible reaction mechanism where azo-pyridine moiety acts activate α-C–H bond Co(II) → Co(I) reduction leads formation aldehyde. generated aldehyde undergoes base-catalyzed C–C result quinolines. potential controls efficiency precatalysts. Thus, complex 3 most anodic best precatalyst among complexes 1–4.

Language: Английский

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