Asymmetric arene hydrogenation: towards sustainability and application

Chemical Society Reviews, Год журнала: 2023, Номер 52(15), С. 4996 - 5012

Опубликована: Янв. 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.

Язык: Английский

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Molybdenum-Catalyzed Asymmetric Hydrogenation of Fused Arenes and Heteroarenes

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(25), С. 11203 - 11214

Опубликована: Июнь 17, 2022

The synthesis of enantioenriched molybdenum precatalysts for the asymmetric hydrogenation substituted quinolines and naphthalenes is described. Three classes pincer ligands with chiral substituents were evaluated as supporting in molybdenum-catalyzed reactions, where oxazoline imino(pyridine) chelates identified optimal. A series 2,6-disubstituted was hydrogenated to decahydroquinolines high diastereo- enantioselectivities. For quinoline derivatives, selective both carbocycle heterocycle observed depending on ring substitution. Spectroscopic mechanistic studies established η6-arene complexes catalyst resting state that partial arises from dissociation substrate coordination sphere prior complete reduction. stereochemical model proposed based relative energies respective prochiral faces arene determined by steric interactions between ligand, rather than through precoordination a heteroatom.

Язык: Английский

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Transfer Hydrogenation of N- and O-Containing Heterocycles Including Pyridines with H₃N–BH₃ Under the Catalysis of the Homogeneous Ruthenium Precatalyst

Organic Letters, Год журнала: 2024, Номер 26(4), С. 866 - 871

Опубликована: Янв. 25, 2024

In this study, we report a transfer hydrogenation protocol that utilizes borane–ammonia (H3N–BH3) as the hydrogen source and commercially available RuCl3·xH2O precatalyst for selective aromatic reduction of quinolines, quinoxalines, pyridines, pyrazines, indoles, benzofurans, furan derivatives to form corresponding alicyclic heterocycles in good excellent isolated yields. Applications straightforward include efficient preparation useful key pharmaceutical intermediates, such donepezil flumequine, including biologically active compound.

Язык: Английский

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Bimetallic Ru/Ru‐Catalyzed Asymmetric One‐Pot Sequential Hydrogenations for the Stereodivergent Synthesis of Chiral Lactones

Advanced Science, Год журнала: 2024, Номер 11(23)

Опубликована: Март 21, 2024

Abstract Asymmetric sequential hydrogenations of α ‐methylene γ ‐ or δ ‐keto carboxylic acids are established in one‐pot using a bimetallic Ru/Ru catalyst system, achieving the stereodivergent synthesis all four stereoisomers both chiral and ‐lactones with two non‐vicinal carbon stereocenters high yields (up to 99%) excellent stereoselectivities >99% ee >20:1 dr). The compatibility Ru systems is investigated detail, it found that basicity reaction system plays key role hydrogenation processes. protocol can be performed on gram‐scale low loading 11000 S/C) resulting products allow for many transformations, particularly several intermediates useful preparation drugs natural products.

Язык: Английский

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Bridging the information gap in organic chemical reactions

Nature Chemistry, Год журнала: 2024, Номер 16(4), С. 491 - 498

Опубликована: Март 28, 2024

Язык: Английский

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Stereodivergent Synthesis of the Vicinal Difluorinated Tetralin of Casdatifan Enabled by Ru-Catalyzed Transfer Hydrogenation

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 13, 2025

We disclose a stereodivergent strategy to prepare vicinal difluorinated tetralins from γ-substituted tetralones via combination of catalyst-controlled transfer hydrogenation and substrate-controlled fluorinations. This process is easily scalable amenable highly functionalized substrates, as demonstrated here in the late-stage synthesis casdatifan, clinical-stage inhibitor hypoxia-inducible factor-2α. Analysis physicochemical properties which features cis-vicinal difluoride, revealed higher level facial polarization compared its trans-vicinal difluoride isomers.

Язык: Английский

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Rhodium-Catalyzed Homogeneous Asymmetric Hydrogenation of Naphthol Derivatives

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 29, 2025

Due to their strong aromaticity and difficulties in chemo-, regio-, enantioselectivity control, asymmetric hydrogenation of naphthol derivatives 1,2,3,4-tetrahydronaphthols has remained a long-standing challenge. Herein, we report the first example homogeneous catalyzed by tethered rhodium-diamine catalysts, affording wide array optically pure high yields with excellent enantioselectivities (up 98% yield >99% ee). Mechanistic studies experimental computational approaches reveal that fluorinated solvent 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) plays vital roles control reactivity selectivity, 1-naphthol is reduced via cascade reaction pathway, including dearomative tautomerization, 1,4-hydride addition, 1,2-hydride addition sequence. A novel synergistic activation mode was proposed which HFIP assists both hydrogen molecule presence base, situ-generated fleeting keto tautomer immediately trapped Rh(III)-H species before it escapes from cage. This protocol provides straightforward practical pathway for synthesis key intermediates several chiral drugs. Particularly, Nadolol, drug treatment hypertension, angina pectoris, congestive heart failure, certain arrhythmias, enantioselectively synthesized time.

Язык: Английский

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Enantio‐ and Diastereoselective, Complete Hydrogenation of Benzofurans by Cascade Catalysis

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(24), С. 13677 - 13681

Опубликована: Апрель 12, 2021

We report an enantio- and diastereoselective, complete hydrogenation of multiply substituted benzofurans in a one-pot cascade catalysis. The developed protocol facilitates the controlled installation up to six new defined stereocenters produces architecturally complex octahydrobenzofurans, prevalent many bioactive molecules. A unique match chiral homogeneous ruthenium-N-heterocyclic carbene situ activated rhodium catalyst from precursor act sequence enable presented process.

Язык: Английский

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Organocatalytic asymmetric synthesis of α-amino esters from sulfoxonium ylides

Chemical Science, Год журнала: 2021, Номер 12(33), С. 11191 - 11196

Опубликована: Янв. 1, 2021

An organocatalytic asymmetric N–H insertion reaction of α-carbonyl sulfoxonium ylides has been developed to provide efficient access α-amino esters without involving a metal carbenoid intermediate.

Язык: Английский

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cis-Selective Hydrogenation of Aryl Germanes: A Direct Approach to Access Saturated Carbo- and Heterocyclic Germanes

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(7), С. 4109 - 4118

Опубликована: Фев. 13, 2023

A catalytic approach of synthesizing the cis-selective saturated carbo- and heterocyclic germanium compounds (3D framework) is reported via hydrogenation readily accessible aromatic germanes (2D framework). Among numerous catalysts tested, Nishimura's catalyst (Rh2O3/PtO2·H2O) exhibited best reactivity with an isolated yield up to 96%. broad range substrates including synthesis unprecedented was explored. This selective strategy could tolerate several functional groups such as −CF3, −OR, −F, −Bpin, −SiR3 groups. The synthesized products demonstrated applications in coupling reactions newly developed aza-Giese-type addition reaction (C–N bond formation) from cyclic germane product. These versatile motifs can have a substantial value organic medicinal chemistry they show orthogonal while competing other partners boranes or silanes, acquiring three-dimensional structure high stability robustness.

Язык: Английский

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