Recent Advances in Homogeneous Catalysts for the Asymmetric Hydrogenation of Heteroarenes

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(23), P. 13834 - 13851

Published: Nov. 12, 2020

The asymmetric hydrogenation of heteroarenes has recently emerged as an effective strategy for the direct access to enantioenriched, saturated heterocycles. Although several homogeneous catalyst systems have been extensively developed with high levels chemo- and stereoselectivity, development mild conditions that allow efficient stereoselective a broad range substrates remains challenge. This Perspective highlights recent advances in catalysis heteroarene inspiration further catalysts, addresses underdeveloped areas limitations current technology.

Language: Английский

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Construction of Monophosphine–Metal Complexes in Privileged Diphosphine-Based Covalent Organic Frameworks for Catalytic Asymmetric Hydrogenation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(11), P. 6100 - 6111

Published: March 10, 2023

Privileged diphosphine ligands that chelate many transition metals to form stable chelation complexes are essential in a variety of catalytic processes. However, the exact identity catalytically active moieties remains ambiguous because chelated metal catalysts may undergo rearrangement during catalysis produce monophosphine-metal complexes, which hard isolate and evaluate activities. By taking advantage isolation two phosphorus atoms, we demonstrate here successful construction chiral monophosphine-Ir/Ru covalent organic frameworks (COFs) for enantioselective hydrogenation. condensation tetraaldehyde enantiopure MeO-BIPHEP linear aromatic diamines, prepare homochiral two-dimensional COFs with ABC stacking, P atoms each separated fixed far apart. Post-synthetic metalations thus afford single-site Ir/Ru-monophosphine catalysts, contrast homogeneous analogues, demonstrated excellent recyclable performance asymmetric hydrogenation quinolines β-ketoesters, affording up 99.9% enantiomeric excess. Owing fact porous catalyst is capable adsorbing concentrating hydrogen, reactions promoted under ambient/medium pressure, typically performed high pressure catalysis. This work not only shows diphosphines can be centers but also provides new strategy types privileged phosphine-based heterogeneous catalysts.

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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Manganese‐Catalyzed Asymmetric Hydrogenation of Quinolines Enabled by π–π Interaction**

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(10), P. 5108 - 5113

Published: Nov. 26, 2020

Abstract The non‐noble metal‐catalyzed asymmetric hydrogenation of N‐heteroaromatics, quinolines, is reported. A new chiral pincer manganese catalyst showed outstanding catalytic activity in the affording high yields and enantioselectivities (up to 97 % ee). turnover number 3840 was reached at a low loading (S/C=4000), which competitive with most effective noble metal catalysts for this reaction. precise regulation enantioselectivity were ensured by π–π interaction.

Language: Английский

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Unmasking the Ligand Effect in Manganese-Catalyzed Hydrogenation: Mechanistic Insight and Catalytic Application

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(43), P. 17337 - 17349

Published: Oct. 21, 2019

Manganese-catalyzed hydrogenation reactions have attracted broad interest since the first report in 2016. Among reported catalytic systems, Mn catalysts supported by tridentate PNP- and NNP-pincer ligands most commonly been used. For example, a number of PNP-Mn pincer for aldehydes, aldimines, ketones, nitriles, esters. Furthermore, various NNP-Mn shown to be active less-reactive substrates such as amides, carbonates, carbamates, urea derivations. These observations indicated that exhibit higher reactivity than their PNP counterparts. Such ligand effect Mn-catalyzed has yet confirmed. Herein, we investigated origin applicability this effect. A combination experimental theoretical investigations showed on complexes were more electron-rich less sterically hindered counterparts, leading series reactions. Inspired hydrogenations, developed N-heterocycles. Specifically, hydrogenated N-heterocycles (32 examples) with up 99% yields, corresponding afforded low under same conditions. This verified is generally applicable both carbonyl noncarbonyl based catalysis.

Language: Английский

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Frustrated Lewis Pairs: Discovery and Overviews in Catalysis

Chinese Journal of Chemistry, Journal Year: 2020, Volume and Issue: 38(11), P. 1360 - 1370

Published: May 9, 2020

Frustrated Lewis Pairs (FLPs) are derived from simple combinations of acids (electron acceptors) and bases donors), in which steric demands prevent forming classical acid‐base adducts. Since 2006, FLP chemistry has emerged as a novel strategy for the design application main‐group development new metal‐free catalytic processes. This been applied to stoichiometric reactivity then extended catalysis. In this review, we briefly summarize representative discoveries developments field catalysis, including hydrogenation, hydrosilylation, reduction CO 2 , transformations alkynes organic derivatives, C—H bond borylation polymerization.

Language: Английский

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Chiral Frustrated Lewis Pair@Metal‐Organic Framework as a New Platform for Heterogeneous Asymmetric Hydrogenation

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(2)

Published: Nov. 9, 2022

Asymmetric hydrogenation, a seminal strategy for the synthesis of chiral molecules, remains largely unmet in terms activation by non-metal sites heterogeneous catalysts. Herein, as demonstrated combined computational and experimental studies, we present general integrating rationally designed molecular frustrated Lewis pair (CFLP) with porous metal-organic framework (MOF) to construct catalyst CFLP@MOF that can efficiently promote asymmetric hydrogenation manner, which first time extends concept from homogeneous system catalysis. Significantly, developed CFLP@MOF, inherits merits both catalysts, high activity/enantio-selectivity excellent recyclability/regenerability. Our work not only advances new platform but also opens avenue design preparation advanced catalysts

Language: Английский

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Dynamic Kinetic Resolution-Based Asymmetric Transfer Hydrogenation of Racemic 2-Substituted Quinolines

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

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Asymmetric Hydrogenation of Ketones and Enones with Chiral Lewis Base Derived Frustrated Lewis Pairs

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(11), P. 4498 - 4504

Published: Dec. 21, 2019

The concept of frustrated Lewis pairs (FLPs) has been widely applied in various research areas, and metal-free hydrogenation undoubtedly belongs to the most significant successful ones. In past decade, great efforts have devoted synthesis chiral boron acids. a sharp contrast, base derived FLPs rarely disclosed for asymmetric hydrogenation. this work, novel type FLP was developed by simple combination oxazoline bases with achiral acids, thus providing promising new direction development future. These proved be highly effective ketones, enones, chromones, giving corresponding products high yields up 95 % ee. Mechanistic studies suggest that hydrogen transfer ketones likely proceeds concerted manner.

Language: Английский

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Controlled partial transfer hydrogenation of quinolines by cobalt-amido cooperative catalysis

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: March 6, 2020

Catalytic hydrogenation or transfer of quinolines was thought to be a direct strategy access dihydroquinolines. However, the challenge is control chemoselectivity and regioselectivity. Here we report an efficient partial system operated by cobalt-amido cooperative catalyst, which converts 1,2-dihydroquinolines reaction with H

Language: Английский

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