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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Organometallic Mn(I) Complexes in Asymmetric Catalytic (Transfer) Hydrogenation and Related Transformations

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(14)

Published: March 7, 2024

Abstract Direct asymmetric hydrogenation (AH) and transfer (ATH) are among the most efficient approaches to produce chiral building blocks. Recently, these types of transformations have witnessed a shift towards use molecular catalysts based on earth‐abundant transition metals due their ready availability, economic advantage, novel properties. With particular regard manganese, catalyst development has seen both efficiency substrate scope in AH ATH greatly improved, with emergence large number well‐defined Mn‐complexes employed this field. The reaction includes C=O bonds, reduction C=N bonds reductive C=C bonds. Herein, our survey area focuses catalytic activity such complexes, versatility routes convert substrates target molecules. We consider collected findings article will be helpful reader by providing an insight into ligand design, thereby aiding future development. Moreover, review is aimed at highlighting remarkable progress made last seven years manganese complexes for enantioselective reduction.

Language: Английский

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Lanthanide/B(C₆F₅)₃-Promoted Hydroboration Reduction of Indoles and Quinolines with Pinacolborane

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(2), P. 887 - 897

Published: Jan. 5, 2024

We have developed a lanthanide/B(C6F5)3-promoted hydroboration reduction of indoles and quinolines with pinacolborane (HBpin). This reaction provides streamlined access to range nitrogen-containing compounds in moderate excellent yields. Large-scale synthesis further transformations bioactive indicate that the method has potential practical applications. Preliminary mechanistic studies suggest amine additives promote formation indole-borane intermediates, proceeds via intermediates HBpin situ-formed BH3 species, followed by protodeborylation process.

Language: Английский

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Unleashing Selective Reduction and Reductive Methylation of N-Heterocycles Using Methanol via Strategic Reaction Condition Modulation

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3008 - 3022

Published: Feb. 5, 2025

Language: Английский

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Sustainable Synthesis of α‐Hydroxycarboxylic Acids by Manganese Catalyzed Acceptorless Dehydrogenative Coupling of Ethylene Glycol and Primary Alcohols**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(10)

Published: Jan. 11, 2023

Herein, we report a straightforward synthesis of valuable α-hydroxycarboxylic acid molecules via an acceptorless dehydrogenative coupling ethylene glycol and primary alcohols. A bench-stable manganese complex catalyzed the reaction, which is scalable, with product being isolated high yields selectivities under mild conditions. The protocol environmentally benign, producing water hydrogen gas as only byproducts. Methanol can also be used C1 source for platform molecule lactic acid, turnover >104 . methodology was to functionalize alcohols derived from natural products fatty acids. Furthermore, it applied synthesizing α-amino α-thiocarboxylic several drugs bioactive molecules, including endogenous metabolites, Danshensu, Enalapril, Lisinopril, Rosmarinic acid. Preliminary mechanistic studies were performed shed light on mechanism involved in reaction.

Language: Английский

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Co(II)-Catalyzed Additive-Free Transfer Hydrogenation of N-Heteroarenes at Room Temperature

Organic Letters, Journal Year: 2024, Volume and Issue: 26(28), P. 6001 - 6005

Published: July 8, 2024

Traditional catalyst development relies on multistep synthesis and isolation of ligand precatalyst. Designing a catalytic system that can be assembled

Language: Английский

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Transfer hydrogenation of pyridinium and quinolinium species using ethanol as a hydrogen source to access saturated N-heterocycles

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(26), P. 4255 - 4258

Published: Jan. 1, 2022

Catalytic transfer hydrogenation (TH) for the reduction of heterocycles is an emerging strategy accessing biologically active saturated N-heterocycles. Herein, we report a TH protocol that utilizes ethanol as renewable hydrogen source and Ir catalyst quinolines pyridines. The reaction promoted by simple amides ligands.

Language: Английский

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Homogeneous cobalt catalyzed reductive formylation of N-heteroarenes with formic acid

Journal of Catalysis, Journal Year: 2022, Volume and Issue: 416, P. 170 - 175

Published: Nov. 9, 2022

Language: Английский

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Hydrogenation of N-Heterocycles by a Well-Defined Phosphine-Free Manganese Catalyst Using Ammonia Borane

Organometallics, Journal Year: 2023, Volume and Issue: 42(23), P. 3385 - 3396

Published: Nov. 27, 2023

Efficient hydrogenation of N-heterocycles employing low-cost and easy-to-access catalysts is highly desirable as the corresponding hydrogenated have significant importance. Herein, we disclosed well-defined phosphine-free Mn-catalyzed effective transfer (TH) various using ammonia borane hydrogen source. In this work, a series Mn(I) complexes were synthesized to investigate importance ligand backbone containing benzimidazole N–H, amine soft sulfur atom. Reactivity studies these Mn revealed that proton-responsive Mn1 complex bearing N–H proton benzimidazole, amine, hemilabile arm was found be most effective. The capability procedure verified by synthesis several biologically active compounds. Mechanistic pathways established performing control reactions kinetic experiments.

Language: Английский

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Dearomative selective reduction of structurally diverse N-heteroarenes enabled by a homogeneous titanium catalyst

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 115937 - 115937

Published: Jan. 1, 2025

Language: Английский

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