Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(11), P. 4386 - 4464

Published: Jan. 1, 2022

The emerging field of organometallic catalysis has shifted towards research on Earth-abundant transition metals due to their ready availability, economic advantage, and novel properties. In this case, manganese, the third most abundant transition-metal in Earth's crust, emerged as one leading competitors. Accordingly, a large number molecularly-defined Mn-complexes been synthesized employed for hydrogenation, dehydrogenation, hydroelementation reactions. regard, catalyst design is based three pillars, namely, metal-ligand bifunctionality, ligand hemilability, redox activity. Indeed, developed catalysts not only differ chelating atoms they possess but also working principles, thereby different turnover numbers product molecules. Hence, critical assessment molecularly defined manganese terms atoms, reaction conditions, mechanistic pathway, significant. Herein, we analyze complexes catalytic activity, versatility allow multiple transformations routes convert substrates target This article will be helpful get significant insight into design, aiding design.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(48), P. 25188 - 25202

Published: June 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.

Language: Английский

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Cobalt-catalyzed dehydrogenative functionalization of alcohols: Progress and future prospect

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 451, P. 214257 - 214257

Published: Oct. 28, 2021

Language: Английский

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Well-Defined Phosphine-Free Manganese(II)-Complex-Catalyzed Synthesis of Quinolines, Pyrroles, and Pyridines

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(13), P. 8351 - 8367

Published: June 21, 2022

Herein, we report a simple, phosphine-free, and inexpensive catalytic system based on manganese(II) complex for synthesizing different important N-heterocycles such as quinolines, pyrroles, pyridines from amino alcohols ketones. Several control experiments, kinetic studies, DFT calculations were carried out to support the plausible reaction mechanism. We also detected two potential intermediates in cycle using ESI-MS analysis. Based these metal-ligand cooperative mechanism was proposed.

Language: Английский

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Synergistic effect between Co single atoms and nanoparticles enables selective synthesis of bio-based benzimidazoles

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 327, P. 122454 - 122454

Published: Feb. 10, 2023

Language: Английский

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Designing Cobalt(II) Complexes for Tandem Dehydrogenative Synthesis of Quinoline and Quinazoline Derivatives

Organic Letters, Journal Year: 2024, Volume and Issue: 26(2), P. 514 - 518

Published: Jan. 9, 2024

In this work, we have constructed three new Co(II) complexes in which steric features govern their structural geometry. The metal ligand-cooperation behavior of the alkoxy arm is utilized to explore catalytic activities these with respect dehydrogenation. A wide range C-3-substituted quinoline and quinazoline derivatives were synthesized high yields. developed protocol's usefulness enhanced by chemoselective transformation different fatty alcohols synthesize heterocycles having distal unsaturation. Various kinetic, mechanistic, control studies conducted comprehend reaction route.

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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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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Well-Defined NNS-Mn Complex Catalyzed Selective Synthesis of C-3 Alkylated Indoles and Bisindolylmethanes Using Alcohols

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(6), P. 3989 - 4000

Published: March 8, 2022

Herein, we demonstrated Mn-catalyzed selective C-3 functionalization of indoles with alcohols. The developed catalyst can also furnish bis(indolyl)methanes from the same set substrates under slightly modified reaction conditions. Mechanistic studies reveal that is going via a borrowing hydrogen pathway. To highlight practical utility, diverse range including nine structurally important drug molecules are synthesized. Furthermore, introduced one-pot cascade strategy for synthesizing functionalized directly 2-aminophenyl ethanol and alcohol.

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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