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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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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Nanoarchitectonics of Non-Noble-Metal-Based Heterogeneous Catalysts for Transfer Hydrogenation Reactions: Detailed Insights on Different Hydrogen Sources

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4211 - 4248

Published: March 5, 2024

Catalytic transfer hydrogenation (CTH) methodology has drawn profound attention of researchers as an economical and environmentally benign alternate to conventional method. Unlike method, CTH exhibits better reaction efficiency atom economy, it makes use simple, easily accessible, low-cost hydrogen sources. Current research on reactions is oriented toward the development non-noble-metal-based catalysts due their high abundance potential large-scale applicability. In this Review, different organic transformation reactions, such nitroarenes, nitriles, alkenes, alkynes, carbonyl compounds, hydrogenolysis, reductive amination, formylation using sources have been summarized comprehensively. addition, synthesis strategies heterogeneous structure–activity relationship involving metal–support interaction, single-atom catalysis, synergistic effect are highlighted. Furthermore, optimization parameters─such temperature, time, solvents, additives─for enhancing catalytic activity selectivity product discussed in detail. This Review provides detailed insights into recent progress made with a specific focus catalyst development, sources, mechanistic exploration.

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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Recent Progress in Transition-Metal-Catalyzed Asymmetric Reductive Amination

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(22), P. 13809 - 13837

Published: Oct. 29, 2021

Asymmetric reductive amination (ARA) of a prochiral carbonyl compound with an amine using H2/hydrogen surrogate is concise and operationally simple method for the synthesis chiral amines. ARA proceeds via condensation group amine/ammonia followed by enantioselective reduction generated intermediate. The activation reductant stereoselective transfer hydrogen to intermediate imine/enamine often mediated transition metal catalyst. Considering wide applications enantiopure amines in pharmaceuticals, agrochemicals, materials, development effective catalysts has been intensively pursued last two decades. Since first report Blaser 1999, this key research area grown significantly recent years, as reflected advances catalyst design, diversifying substrate scope better mechanistic understanding. Several highly efficient general methodologies applicable challenging partners have demonstrated, providing ready access variety In Review, we present progress featuring diverse employing metal-catalysts. This Review provides organized critical discussion on engineering evolution, expanding susbstrate insights. To conclude, remaining challenges opportunities are also highlighted.

Language: Английский

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Late-Stage Diversification: A Motivating Force in Organic Synthesis

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(41), P. 16890 - 16901

Published: Oct. 6, 2021

Interest in therapeutic discovery typically drives the preparation of natural product analogs, but these undertakings contribute significant advances for synthetic chemistry as well. The need a highly efficient and scalable route to complex molecular scaffold diversification frequently inspires new methodological development or unique application existing methods on structurally intricate systems. Additionally, planning with an aim toward late-stage can provide access otherwise unavailable compounds facilitate molecules diverse patterns substitution around shared carbon framework. For reasons among others, programs dedicated frameworks other scaffolds have been increasing popularity, trend likely continue given their fruitfulness breadth impact. In this Perspective, we discuss our experience using guiding principle synthesis analogs reflect impact such efforts future molecule synthesis.

Language: Английский

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Recent developments in enantio- and diastereoselective hydrogenation of N-heteroaromatic compounds

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(9), P. 1794 - 1827

Published: Jan. 1, 2022

The enantioselective and diastereoselective hydrogenation of N-heteroaromatic compounds is an efficient strategy to access chirally enriched cyclic heterocycles, which often possess highly bio-active properties. This strategy, however, has only been established in recent times. part due the challenges high stability aromatic presence heteroatoms that have potential poison chiral catalysts. Additionally, are a structurally diverse family substrates, each group showing distinct reactivity hydrogenation. Advances years allowed various compounds, including pyridines, indoles, quinolines, isoquinolines, quinoxalines imidazoles, be hydrogenated with good excellent enantioselectivity under appropriate reaction conditions. Transition-metal catalysis, utilising iridium, ruthenium, rhodium, palladium complexes, found play important role this field. More recently, organocatalysis shown for certain compounds. review provides analysis developments importance these molecules their applications drug discovery highlighted throughout review.

Language: Английский

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Manganese‐Catalyzed Asymmetric Hydrogenation of 3H‐Indoles

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(20)

Published: March 3, 2022

The asymmetric hydrogenation (AH) of 3H-indoles represents an ideal approach to the synthesis useful chiral indoline scaffolds. However, very few catalytic systems based on precious metals have been developed realize this challenging reaction. Herein, we report a Mn-catalyzed AH with excellent yields and enantioselectivities. kinetic resolution racemic by was also achieved high s-factors construct quaternary stereocenters. Many acid-sensitive functional groups, which cannot be tolerated when using state-of-the-art ruthenium catalyst, were compatible manganese catalysis. This new process expands scope transformation highlights uniqueness earth-abundant metal reaction could proceed catalyst loadings at parts per million (ppm) level exceptional turnover number 72 350. is highest value yet reported for metal-catalyzed

Language: Английский

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