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

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4607 - 4647

Published: Jan. 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.

Language: Английский

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Advancements in multifunctional manganese complexes for catalytic hydrogen transfer reactions

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(69), P. 8534 - 8549

Published: Jan. 1, 2021

Manganese catalyzed hydrogen transfer reactions enabled net reductions and cascade CC- CN-bond formation reactions. The success is aided by multifunctional ligand design namely metal–ligand bifunctionality, hemilability, redox non-innocence.

Language: Английский

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Towards ligand simplification in manganese-catalyzed hydrogenation and hydrosilylation processes

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 458, P. 214421 - 214421

Published: Jan. 31, 2022

Language: Английский

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Recent Advances in Nonprecious Metal Catalysis

Organic Process Research & Development, Journal Year: 2023, Volume and Issue: 27(3), P. 423 - 447

Published: Feb. 17, 2023

Nonprecious-metal-catalyzed alternatives to powerful precious metal transformations are of increasing interest in academia and the pharmaceutical industry due lower cost, better sustainability, toxicity. With continual growth broad field nonprecious catalysis (NPMC), we have chosen highlight selected articles published from March June 2022 which intended examples NPMC that feel may be especially relevant development. We aim inspire academic industrial innovation through discussion herein.

Language: Английский

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

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

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Manganese‐Catalyzed Asymmetric Formal Hydroamination of Allylic Alcohols: A Remarkable Macrocyclic Ligand Effect

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(26)

Published: April 19, 2022

A unique family of chiral peraza N6 -macrocyclic ligands, which are conformationally rigid and have a tunable saddle-shaped cavity, is described. Utilizing their manganese(I) complexes, the first example earth-abundant transition metal-catalyzed asymmetric formal anti-Markovnikov hydroamination allylic alcohols was realized, providing practical access to synthetically important γ-amino in excellent yields enantioselectivities (up 99 % yield 98 ee). The single-crystal structure MnI complex indicates that manganese atom coordinates with dialkylamine moiety bidentate fashion. Further DFT calculations revealed five six nitrogen atoms ligand were engaged multiple noncovalent interactions Mn, an isopropanol molecule, β-amino ketone intermediate via coordination, hydrogen bonding, and/or CH⋅⋅⋅π state, showing remarkable role macrocyclic framework.

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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Homogeneous Manganese-Catalyzed Hydrofunctionalizations of Alkenes and Alkynes: Catalytic and Mechanistic Tendencies

ACS Omega, Journal Year: 2022, Volume and Issue: 7(42), P. 37008 - 37038

Published: Oct. 11, 2022

In recent years, many manganese-based homogeneous catalytic precursors have been developed as powerful alternatives in organic synthesis. Among these, the hydrofunctionalizations of unsaturated C–C bonds correspond to outstanding ways afford compounds with more versatile functional groups, which are commonly used building blocks production fine chemicals and feedstock for industrial field. Herein, we present an account Mn-catalyzed alkenes alkynes main objective finding mechanistic tendencies that could serve a platform works come.

Language: Английский

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Nickel-catalyzed hydroarylation reaction: a useful tool in organic synthesis

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(18), P. 5074 - 5103

Published: Jan. 1, 2022

The nickel-catalyzed hydroarylation reaction opens up new routes to access complex organic compounds in a highly regio and stereoselective fashion from easily available precursors, such as olefin, alkyne, arene, aryl halide, boronic acid.

Language: Английский

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