Amino Acid Derived Chiral Aminobenzimidazole Manganese Catalysts for Asymmetric Transfer Hydrogenation of Ketones DOI
Lixian Wang, Jin Lin, Qiangsheng Sun

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(13), P. 8033 - 8041

Published: June 17, 2021

A series of Mn(I) catalysts with chiral bidentate benzimidazoles derived from easily available amino acids has been developed. These types phosphine-free Mn demonstrate high activity and enantioselectivity in asymmetric transfer hydrogenation (ATH) for a broad range ketone substrates. bulkier substrate, such as 2,6-dichloro-3-fluoroacetophenone, can be converted into the drug intermediate alcohol up to 90% yield 92% ee (e.g., crizotinib). On basis experimental DFT studies, possible mechanism this Mn-catalyzed ATH is also proposed. calculations further render plausible model enantiocontrol hydrogenation, which π–π stacking interaction between catalyst substrate plays an important role.

Language: Английский

Recent Advances in the Enantioselective Synthesis of Chiral Amines via Transition Metal-Catalyzed Asymmetric Hydrogenation DOI Creative Commons
Albert Cabré, Xavier Verdaguer, Antoni Riéra

et al.

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

Citations

297
Chiral Tridentate Ligands in Transition Metal-Catalyzed Asymmetric Hydrogenation DOI
Heng Wang, Jialin Wen, Xumu Zhang

et al.

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

Citations

196
Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions DOI
Kuhali Das, Satyadeep Waiba, Akash Jana

et al.

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

Citations

160
Green Regenerative Hydrogel Wound Dressing Functionalized by Natural Drug‐Food Homologous Small Molecule Self‐Assembled Nanospheres DOI
Xinyu Sun,

Jia Pei,

Hui Zhang

et al.

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

Citations

123
Nickel-catalysed asymmetric hydrogenation of oximes DOI
Bowen Li, Jianzhong Chen, Dan Liu

et al.

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

Published: June 13, 2022

Language: Английский

Citations

92
Asymmetric arene hydrogenation: towards sustainability and application DOI Creative Commons

Lukas Lückemeier,

Marco Pierau,

Frank Glorius

et al.

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

Citations

56
Differentiating enantiomers by directional rotation of ions in a mass spectrometer DOI
X. K. Zhou, Zhuofan Wang, Shuai Li

et al.

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

Citations

19
Chemoselective Heterogeneous Hydrogenation of Sulfur Containing Quinolines under Mild Conditions DOI Creative Commons

Lukas Lückemeier,

Thijs De Vos,

Lisa Schlichter

et al.

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

Citations

19
Dynamic Kinetic Resolution-Based Asymmetric Transfer Hydrogenation of Racemic 2-Substituted Quinolines DOI
Liang Meng,

Xian Du,

Jian Jun Lin

et al.

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

Published: Jan. 22, 2025

The synthesis of chiral tetrahydroquinolines (THQs) has garnered significant interest from medicinal chemists due to their frequent presence as pharmacophores in bioactive compounds. While existing synthetic methods have primarily focused on THQs with single or multiple endocyclic centers, the selective construction both endo- and exo-cyclic centers remains a challenge that requires further development. This study introduces dynamic kinetic resolution (DKR)-based transfer hydrogenation racemic 2-substituted quinolines, which yields structurally novel consecutive excellent stereoselectivities (59 examples, generally >20:1 dr >90% ee, up three stereocenters). Our approach offers mechanistically method for asymmetric transformation electron-deficient aromatic N-heterocycles presents an innovative way expand N-heterocycle chemical space chemistry.

Language: Английский

Citations

3
Enantioselective Synthesis of Chiral 1,4-Dihydroquinolines via Iridium-Catalyzed Asymmetric Partial Hydrogenation of Quinolines DOI

Chang-Liang Zhu,

Xueyuan Yan,

Huai‐Yu Bin

et al.

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

Citations

3