Recent advances in sustainable synthesis of N-heterocycles following acceptorless dehydrogenative coupling protocol using alcohols

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(11), С. 2673 - 2709

Опубликована: Янв. 1, 2021

In this review, we have summarized various aspects of homogeneous and heterogeneously catalyzed recent advancements in the synthesis heterocycles following ADC approach.

Язык: Английский

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Synthesis of N‐Heterocycles via Oxidant‐Free Dehydrocyclization of Alcohols Using Heterogeneous Catalysts

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(48), С. 25188 - 25202

Опубликована: Июнь 17, 2021

N-Heterocycles, such as pyrroles, pyrimidines, quinazolines, and quinoxalines, are important building blocks for organic chemistry the fine-chemical industry. For their synthesis, catalytic borrowing hydrogen acceptorless dehydrogenative coupling reactions of alcohols sustainable reagents have received significant attention in recent years. To overcome problems product separation catalyst reusability, several metal-based heterogeneous catalysts been reported to achieve these transformations with good yields selectivity. In this Minireview, we summarize developments using both noble non-noble synthesize N-heterocycles from N-nucleophiles via dehydrogenation or methodologies. Furthermore, Minireview introduces strategies preparation functionalization corresponding catalysts, discusses reaction mechanisms roles metal electronic states, influence support Lewis acid-base properties on reactions.

Язык: Английский

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Manganese(I)-Catalyzed Sustainable Synthesis of Quinoxaline and Quinazoline Derivatives with the Liberation of Dihydrogen

The Journal of Organic Chemistry, Год журнала: 2020, Номер 85(11), С. 7181 - 7191

Опубликована: Май 13, 2020

Direct synthesis of N-heterocycles via the acceptorless dehydrogenative coupling is very challenging and scarcely reported under 3d transition-metal catalysis. Here, we have developed an efficient Mn(I)-catalyzed sustainable various quinoxalines from 1,2-diaminobenzenes 1,2-diols reaction. Further, this strategy was successfully applied for unprecedented quinazolines by reaction 2-aminobenzyl alcohol with primary amides. The present protocol provides atom-economical route quinoxaline quinazoline derivatives employing earth-abundant manganese salt simple phosphine-free NNN-tridentate ligand.

Язык: Английский

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Homogeneous Nickel-Catalyzed Sustainable Synthesis of Quinoline and Quinoxaline under Aerobic Conditions

The Journal of Organic Chemistry, Год журнала: 2020, Номер 85(23), С. 14971 - 14979

Опубликована: Ноя. 11, 2020

Dehydrogenative coupling-based reactions have emerged as an efficient route toward the synthesis of a plethora heterocyclic rings. Herein, we report efficacious, nickel-catalyzed two important heterocycles such quinoline and quinoxaline. The catalyst is molecularly defined, phosphine-free, can operate at mild reaction temperature 80 °C. Both be easily assembled via double dehydrogenative coupling, starting from 2-aminobenzyl alcohol/1-phenylethanol diamine/diol, respectively, in shorter span time. This environmentally benign synthetic protocol employing inexpensive rival many other transition-metal systems that been developed for fabrication putative heterocycles. Mechanistically, dehydrogenation secondary alcohol follows clean pseudo-first-order kinetics exhibits sizable kinetic isotope effect. Intriguingly, this provides example storing trapped hydrogen ligand backbone, avoiding metal-hydride formation. Easy regeneration oxidized form under aerobic/O2 oxidation makes eco-friendly easy to handle.

Язык: Английский

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Recent advances in nickel-catalyzed C–C and C–N bond formation via HA and ADC reactions

Organic & Biomolecular Chemistry, Год журнала: 2021, Номер 19(19), С. 4213 - 4227

Опубликована: Янв. 1, 2021

In this review article, recent advances in nickel-catalyzed hydrogen auto-transfer (HA) and acceptorless dehydrogenative coupling (ADC) reactions for the construction of C–C C–N bonds have been discussed.

Язык: Английский

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Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds

Chemical Society Reviews, Год журнала: 2024, Номер 53(9), С. 4607 - 4647

Опубликована: Янв. 1, 2024

This review collectively discussed the utilisation of alcohols in various organic transformations and their application toward intermediates drugs, drug derivatives natural product-like molecules.

Язык: Английский

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Valorization of bio-renewable glycerol by catalytic amination reactions

Green Chemistry, Год журнала: 2024, Номер 26(6), С. 3021 - 3038

Опубликована: Янв. 1, 2024

Production of value-added chemicals from renewable feedstocks is an attractive platform to alleviate the shortage petroleum resources and minimize CO 2 emissions.

Язык: Английский

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Recent Progress in the Synthesis of Heterocycles through Base Metal‐Catalyzed Acceptorless Dehydrogenative and Borrowing Hydrogen Approach

European Journal of Organic Chemistry, Год журнала: 2021, Номер 2021(26), С. 3690 - 3720

Опубликована: Июнь 15, 2021

Abstract Development in the area of acceptorless dehydrogenation (AD) and borrowing hydrogen (BH) catalysis emerge as one potential tools for various C−C C‐heteroatom bond forming reactions. Alcohols, which are important lignocellulosic biomass products, act pivotal electrophilic coupling partners such processes interestingly only H 2 or O is eliminated a byproduct. Initially, was developed by use noble metal catalysts. Recently, base metals Mn, Fe, Co, Ni proved to be environmentally benign inexpensive alternatives application AD BH methods. This transition catalyzed approaches also allow access toward plethora structurally heterocyclic molecules via atom economical strategy. Herein, we summarize current rising expansion heterocycles synthesis through hydrogenation

Язык: Английский

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Iron-Catalyzed Hydrogen Transfer Reduction of Nitroarenes with Alcohols: Synthesis of Imines and Aza Heterocycles

The Journal of Organic Chemistry, Год журнала: 2020, Номер 86(1), С. 1023 - 1036

Опубликована: Дек. 16, 2020

A straightforward and selective reduction of nitroarenes with various alcohols was efficiently developed using an iron catalyst via a hydrogen transfer methodology. This protocol led specifically to imines in 30–91% yields, good functional group tolerance. Noticeably, starting from o-nitroaniline derivatives, the presence alcohols, benzimidazoles can be obtained 64–72% yields when reaction performed additional oxidant, DDQ, quinoxalines were prepared 1,2-diols 28–96% yields. methodology, unprecedented at for imines, also provides sustainable alternative preparation benzimidazoles.

Язык: 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, Год журнала: 2021, Номер 2021(46), С. 6206 - 6223

Опубликована: Ноя. 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.

Язык: Английский

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