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

Chemical Reviews, Год журнала: 2021, Номер 122(1), С. 269 - 339

Опубликована: Окт. 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

Язык: Английский

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Asymmetric hydrogenation catalyzed by first-row transition metal complexes

Chemical Society Reviews, Год журнала: 2021, Номер 50(5), С. 3211 - 3237

Опубликована: Янв. 1, 2021

This review focuses on asymmetric direct and transfer hydrogenation with first-row transition metal complexes. The reaction mechanisms the models of enantiomeric induction were summarized emphasized.

Язык: Английский

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Nickel-catalysed asymmetric hydrogenation of oximes

Nature Chemistry, Год журнала: 2022, Номер 14(8), С. 920 - 927

Опубликована: Июнь 13, 2022

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(10), С. 5108 - 5113

Опубликована: Ноя. 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.

Язык: Английский

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Metal-Catalyzed Asymmetric Hydrogenation of C═N Bonds

ACS Catalysis, Год журнала: 2020, Номер 11(1), С. 215 - 247

Опубликована: Дек. 17, 2020

This Review recaps the achievements in field of metal-catalyzed asymmetric direct hydrogenation nonactivated and activated imines. A summary reported catalytic systems with corresponding reactivity, selectivity, limitations is given including a discussion about effects some reaction conditions on enantioselectivity imine hydrogenation. An analysis proposed mechanisms discussed.

Язык: Английский

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Ni-catalyzed asymmetric hydrogenation of N-aryl imino esters for the efficient synthesis of chiral α-aryl glycines

Nature Communications, Год журнала: 2020, Номер 11(1)

Опубликована: Ноя. 23, 2020

Abstract Chiral α-aryl glycines play a key role in the preparation of some bioactive products, however, their catalytic asymmetric synthesis is far from being satisfactory. Herein, we report an efficient nickel-catalyzed hydrogenation N -aryl imino esters, affording chiral high yields and enantioselectivities (up to 98% ee). The can be conducted on gram scale with substrate/catalyst ratio up 2000. obtained - p -methoxyphenyl glycine derivatives are not only directly useful secondary amino acid esters but also easily deprotected by treatment cerium ammonium nitrate for further transformations several widely used molecules including drug intermediates ligands. Formation Ni-H species detected 1 H NMR. Computational results indicate that stereo selection determined during approach substrate catalyst.

Язык: Английский

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Nickel‐Catalyzed Asymmetric Hydrogenation of 2‐Amidoacrylates

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(13), С. 5371 - 5375

Опубликована: Янв. 20, 2020

Earth-abundant nickel, coordinated with a suitable chiral bisphosphine ligand, was found to be an efficient catalyst for the asymmetric hydrogenation of 2-amidoacrylates, affording α-amino acid esters in quantitative yields and excellent enantioselectivity (up 96 % ee). The active component studied by NMR HRMS, which helped us realize high catalytic efficiency on gram scale low loading (S/C=2000). hydrogenated products could simply converted into acids, β-amino alcohols, their bioactive derivatives. Furthermore, mechanism investigated using deuterium-labeling experiments computational calculations.

Язык: Английский

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Cobalt-catalyzed highly enantioselective hydrogenation of α,β-unsaturated carboxylic acids

Nature Communications, Год журнала: 2020, Номер 11(1)

Опубликована: Июнь 26, 2020

Asymmetric hydrogenation of α,β-unsaturated acids catalyzed by noble metals has been well established, whereas, the asymmetric with earth-abundant-metal was rarely reported. Here, we describe a cobalt-catalyzed carboxylic acids. By using chiral cobalt catalyst bearing electron-donating diphosphine ligand, high activity (up to 1860 TON) and excellent enantioselectivity >99% ee) are observed. Furthermore, is successfully applied broad spectrum acids, such as various α-aryl α-alkyl cinnamic acid derivatives, α-oxy-functionalized α-substituted acrylic heterocyclic (30 examples). The synthetic utility protocol highlighted synthesis key intermediates for drugs (6 cases). Preliminary mechanistic studies reveal that carboxy group may be involved in control reactivity through an interaction metal centre.

Язык: 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, Год журнала: 2021, Номер 60(20), С. 11384 - 11390

Опубликована: Фев. 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.

Язык: Английский

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Mechanistic Study of Ni and Cu Dual Catalyst for Asymmetric C–C Bond Formation; Asymmetric Coupling of 1,3-Dienes with C-nucleophiles to Construct Vicinal Stereocenters

ACS Catalysis, Год журнала: 2021, Номер 11(11), С. 6643 - 6655

Опубликована: Май 21, 2021

We report details of the reaction mechanism for a coupling 1,3-dienes with C-nucleophiles that was catalyzed by Ni/Cu cooperative catalyst system using Ni(cod)2 and [Cu(CH3CN)4]PF6 in presence chiral JOSIPHOS-type bisphosphine ligand iPr2NEt, providing direct access to highly valuable vicinal quaternary tertiary stereocenters high enantio- diastereoselectivity. The bimetallic exhibited broad substrate scope, including both cyclic/acyclic stabilized nucleophiles aryl-/alkyl-substituted 1,3-dienes. elucidated depth isolating characterizing four key complexes nickel copper conducting deuterium labeling experiments, kinetic studies, density functional theory calculations. turnover-limiting step this is proton-transfer diene-coordinated Ni complex 6 from cationic Cu 8 yield π-allyl 7 enolate 9, respectively. stereoselectivity also clarified according single-point calculations intermediates 9.

Язык: Английский

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