Recent Advances in the Enantioselective Synthesis of Chiral Amines via Transition Metal-Catalyzed Asymmetric Hydrogenation

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(1), P. 269 - 339

Published: Oct. 22, 2021

Chiral amines are key structural motifs present in a wide variety of natural products, drugs, and other biologically active compounds. During the past decade, significant advances have been made with respect to enantioselective synthesis chiral amines, many them based on catalytic asymmetric hydrogenation (AH). The review covers use AH bearing stereogenic center either α, β, or γ position nitrogen atom, reported from 2010 2020. Therefore, we provide an overview recent imines, enamides, enamines, allyl N-heteroaromatic

Language: Английский

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Chiral Tridentate Ligands in Transition Metal-Catalyzed Asymmetric Hydrogenation

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(13), P. 7530 - 7567

Published: May 20, 2021

Asymmetric hydrogenation (AH) of double bonds has been one the most effective methods for preparation chiral molecules and synthesis important building blocks. In past 60 years, noble metals with bidentate ligands have shown marvelous reactivity enantioselectivity in asymmetric a series prochiral substrates. recent developing tridentate played an increasingly role AH. With modular frameworks variety functionalities on side arms, ligand complexes enable both reactivities stereoselectivities. Although great achievements made metal catalysts since 1990s, design earth abundant still high demand. This review summarizes development homogeneous hydrogenation. The philosophy reaction mechanisms are highlighted discussed as well.

Language: Английский

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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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Green Regenerative Hydrogel Wound Dressing Functionalized by Natural Drug‐Food Homologous Small Molecule Self‐Assembled Nanospheres

Advanced Functional Materials, Journal Year: 2021, Volume and Issue: 32(7)

Published: Nov. 5, 2021

Abstract The goal of regenerative wound healing dressings is to restore tissue function back normal physiological activity and accelerate skin regeneration at sites. optimal strategy achieve this purpose requires a balance between material functionality, degradation, safety, regrowth. Herein, for the first time, an ultrasonic‐triggered irreversible tending equilibrium self‐assembly ionic cross‐linking codriven proposed producing multifunctional cinnamaldehyde‐tannic acid‐zinc acetate nanospheres (CA‐TA‐ZA NSs), realizing fusion hydrophilic hydrophobic drug‐food small molecules. Moreover, novel “all‐in‐one” chitosan (CS)‐based hydrogel functionalized by introducing molecules self‐assembled CA‐TA‐ZA NSs 3D network structures CS designed, integrating excellent antibacterial, antioxidant, anti‐inflammatory reducing oxidative stress damage abilities. Additionally, CS‐based can realize rapid in situ gelation sites completely cover irregular wounds. All these superiorities enable clean microenvironment, induce remodeling, promote blood vessel repair hair follicle regeneration, immune system activity, healing. Therefore, study offers new perspective design advanced functional materials with great application potential biomedical field.

Language: Английский

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Nickel-catalysed asymmetric hydrogenation of oximes

Nature Chemistry, Journal Year: 2022, Volume and Issue: 14(8), P. 920 - 927

Published: June 13, 2022

Language: Английский

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Asymmetric arene hydrogenation: towards sustainability and application

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(15), P. 4996 - 5012

Published: Jan. 1, 2023

This review summarises the state-of-the-art in transition-metal catalysed asymmetric hydrogenation of (hetero)arenes and highlights recent advances with a special focus on sustainability while also addressing its shortcomings.

Language: Английский

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Differentiating enantiomers by directional rotation of ions in a mass spectrometer

Science, Journal Year: 2024, Volume and Issue: 383(6683), P. 612 - 618

Published: Feb. 8, 2024

Conventional mass spectrometry does not distinguish between enantiomers, or mirror-image isomers. Here we report a technique to break the chiral symmetry and differentiate enantiomers by inducing directional rotation of gas-phase ions. Dual alternating current excitations were applied manipulate motions trapped ions, including around center macro movement trap. Differences in collision cross section induced, which could be measured ion cloud profiling at high resolutions above 10,000. High-field mobility tandem analyses combined implemented using miniature trap spectrometer. The effectiveness developed method was demonstrated with variety organic compounds amino acids, sugars, several drug molecules, as well proof-of-principle ligand optimization study for asymmetric hydrogenation.

Language: Английский

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Chemoselective Heterogeneous Hydrogenation of Sulfur Containing Quinolines under Mild Conditions

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 5864 - 5871

Published: Feb. 20, 2024

Sulfur, alongside oxygen and nitrogen, holds a prominent position as one of the key heteroatoms in nature medicinal chemistry. Its significance stems from its ability to adopt different oxidation states, rendering it valuable both polarity handle hydrogen bond donor/acceptor. Nevertheless, poisonous free electron pairs makes sulfur containing substrates inaccessible for many catalytic protocols. Strong (at low temperatures) irreversible chemisorption catalyst's surface is particular detrimental heterogeneous catalysts, possessing only few catalytically active sites. Herein, we present novel Ru-S catalyst that tolerates multiple functionalities, including thioethers, thiophenes, sulfoxides, sulfones, sulfonamides, sulfoximines, hydrogenation quinolines. The utility products was further demonstrated by subsequent diversifications functionalities.

Language: Английский

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Enantioselective Synthesis of Chiral 1,4-Dihydroquinolines via Iridium-Catalyzed Asymmetric Partial Hydrogenation of Quinolines

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Chiral 1,4-dihydroquinolines are frequently found in natural products and pharmaceuticals, yet a generally useful route for their synthesis remains elusive. Here, we present an asymmetric partial hydrogenation strategy to access enantioenriched from quinolines. Our involves incorporating ester group at position 3 of the quinoline ring, thereby enhancing electronic deficiency polarity C3–C4 double bond. Employing chiral Ir-SpiroPAP catalyst facilitated wide variety 4-substituted 3-ethoxycarbonylquinolines, yielding high yields (up 95%) with exceptional enantioselectivity efficiency 99% ee 1840 TONs). Noteworthy its scalability practicality, method provides robust avenue valuable compounds such as 9-aryl aza-podophyllotoxins melatonin MT2 receptor modulators. Density functional theory calculations were performed gain insights into reaction mechanism origins enantioselectivity.

Language: Английский

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Enantioselective Hydrogenation of Tetrasubstituted α,β‐Unsaturated Carboxylic Acids Enabled by Cobalt(II) Catalysis: Scope and Mechanistic Insights

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(20), P. 11384 - 11390

Published: Feb. 19, 2021

Abstract Chiral carboxylic acids are important compounds because of their prevalence in pharmaceuticals, natural products and agrochemicals. Asymmetric hydrogenation α,β‐unsaturated has been widely recognized as one the most efficient synthetic approaches to afford such compounds. Although related asymmetric di‐ trisubstituted unsaturated with noble metals is well established, challenging tetrasubstituted rarely reported. We demonstrate enantioselective cyclic acyclic via cobalt(II) catalysis. This protocol showed broad substrate scope gave chiral good yields excellent enantiocontrol (up 98 % yield 99 ee ). Combined experimental computational mechanistic studies support a Co II catalytic cycle involving migratory insertion σ‐bond metathesis processes. DFT calculations reveal that enantioselectivity may originate from steric effect between phenyl groups ligand substrate.

Language: Английский

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