Late-Stage C–H Functionalization of Azines

Chemical Reviews, Год журнала: 2023, Номер 123(12), С. 7655 - 7691

Опубликована: Май 3, 2023

Azines, such as pyridines, quinolines, pyrimidines, and pyridazines, are widespread components of pharmaceuticals. Their occurrence derives from a suite physiochemical properties that match key criteria in drug design is tunable by varying their substituents. Developments synthetic chemistry, therefore, directly impact these efforts, methods can install various groups azine C–H bonds particularly valuable. Furthermore, there growing interest late-stage functionalization (LSF) reactions focus on advanced candidate compounds often complex structures with multiple heterocycles, functional groups, reactive sites. Because factors electron-deficient nature the effects Lewis basic N atom, distinct arene counterparts, application LSF contexts difficult. However, have been many significant advances reactions, this review will describe progress, much which has occurred over past decade. It possible to categorize radical addition processes, metal-catalyzed activation transformations occurring via dearomatized intermediates. Substantial variation reaction within each category indicates both rich reactivity heterocycles creativity approaches involved.

Язык: Английский

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Visible light-induced functionalization of indazole and pyrazole: a recent update

Chemical Communications, Год журнала: 2022, Номер 58(28), С. 4435 - 4455

Опубликована: Янв. 1, 2022

Indazole and pyrazole are renowned as a prodigious class of heterocycles having versatile uses in medicinal well industrial chemistry. Considering sustainable approaches, recently, photocatalysis has become an indispensable tool organic chemistry due to its application for the activation small molecules use clean energy source. In this review, we have highlighted metal-based photocatalysts, photoredox catalysts, transfer photocatalysts electron-donor-acceptor complexes functionalization indazole pyrazole. This perspective is arranged based on types reactions A detailed discussion regarding reaction mechanism each given provide comprehensive guide reader. Finally, summary existing challenges future outlook towards development efficient photocatalytic methods these also presented.

Язык: Английский

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Visible-light-induced metal-free coupling of C(sp³)–H sources with heteroarenes

Green Chemistry, Год журнала: 2022, Номер 24(8), С. 3056 - 3080

Опубликована: Янв. 1, 2022

This critical review chronologically summarizes the metal-free coupling methodologies of C(sp 3 )–H sources with heteroarenes induced by visible light. The articles which are published up to January 2022 on this topic enclosed here.

Язык: Английский

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Visible Light Photoredox-Catalyzed Direct C–H Arylation of Quinoxalin-2(1H)-ones with Diaryliodonium Salts

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(16), С. 10947 - 10957

Опубликована: Авг. 4, 2022

A photoredox-catalyzed direct arylation of quinoxalin-2-(1H)-ones using diaryliodonium triflates as the convenient, stable, and cheap aryl source is described. broad variety are shown to react with structurally electronically diverse triflates, allowing efficient access a wide pharmaceutically important 3-arylquinoxalin-2-(1H)-ones. The presented method attractive regard operational simplicity, mild conditions, scope, scalability, high functional group tolerance.

Язык: Английский

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Visible light-induced organophotoredox-catalyzed difunctionalization of alkenes and alkynes

Green Chemistry, Год журнала: 2023, Номер 25(21), С. 8459 - 8493

Опубликована: Янв. 1, 2023

This review comprehensively summarizes visible light-induced difunctionalization strategies for alkene and alkyne systems in metal-free conditions with literature coverage up to July 2023.

Язык: Английский

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Photodecarboxylative C–H Alkylation of Azauracils with N-(Acyloxy)phthalimides

Organic Letters, Год журнала: 2023, Номер 25(20), С. 3739 - 3744

Опубликована: Май 15, 2023

We disclose a transition-metal-free NaI/PPh3-mediated direct C-H alkylation of azauracils using N-(acyloxy)pthalimides (NHPIs) as readily available alkyl surrogates under visible light irradiation. Detailed mechanistic studies reveal formation photoactivated electron donor-acceptor (EDA) complex between NaI/PPh3, TMEDA, and NHPI ester establish the crucial role TMEDA in increasing activity photoredox system. The reaction demonstrates broad scope, scalability, appreciable functional group tolerance. A variety are shown to undergo by primary, secondary, tertiary esters mild conditions, furnishing desired products good excellent yields.

Язык: Английский

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Visible-light-induced cascade reaction: a sustainable approach towards molecular complexity

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(8), С. 1591 - 1628

Опубликована: Янв. 1, 2023

Photoredox catalysis has demonstrated rapid evolution in the field of synthetic organic chemistry. On other hand, splendour cascade reactions providing complex molecular architectures renders them a cutting-edge research area. Therefore, merging photocatalysis with synthesis brings out paradigm immense potential. The development photocascade for target molecule particular skeleton and stereochemical framework presents certain challenges but provides robust environmentally benign alternative. This comprehensive review assembles all accomplishments highlights visible-light-induced literature coverage up to October 2022.

Язык: Английский

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A General Electron Donor–Acceptor Photoactivation Platform of Diaryliodonium Reagents: Arylation of Heterocycles

Organic Letters, Год журнала: 2023, Номер 25(46), С. 8290 - 8295

Опубликована: Ноя. 14, 2023

We report a photoredox system comprising sodium iodide, triphenyl phosphine, and N,N,N',N'-tetramethylethylenediamine (TMEDA) that can form self-assembled tetrameric electron donor-acceptor (EDA) complex with diaryliodonium reagents (DAIRs) furnish aryl radicals upon visible light irradiation. This practical mode of activation DAIRs enables arylation an array heterocycles under mild conditions to provide the respective heteroaryl-(hetero)aryl assembly in moderate excellent yields. Detailed mechanistic investigations photophysical DFT studies provided insight into reaction mechanism.

Язык: Английский

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Late‐Stage Functionalisation of Pyridine‐Containing Bioactive Molecules: Recent Strategies and Perspectives

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(16)

Опубликована: Фев. 21, 2023

Abstract Late‐Stage Functionalisation (LSF) is an innovative technique that has been successfully applied to the C−H diversification of pharmaceuticals. However, LSF pyridine ring in drug‐like molecules often unselective. As a result, mixture structurally related products obtained, thus making purification tedious and time‐consuming. This review shines light on recent strategies addressing selectivity issue complex natural or drugs containing moiety. Specifically, we have reviewed efforts reported both academia industries with hope providing guide for elaborated pyridines.

Язык: Английский

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Organophotoredox-Catalyzed Arylation and Aryl Sulfonylation of Morita–Baylis–Hillman Acetates with Diaryliodonium Reagents

Organic Letters, Год журнала: 2023, Номер 25(43), С. 7900 - 7905

Опубликована: Окт. 26, 2023

We report an organophotoredox-catalyzed stereoselective allylic arylation of MBH acetates with a palette diaryliodonium triflates (DAIRs) to provide the corresponding trisubstituted alkenes in moderate good yields. The method could be extended three-component coupling involving 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) adduct (DABSO) as sulfur dioxide surrogate for synthesis biologically relevant sulfones. Both these reactions were carried out under mild conditions featuring broad scope, robustness, and appreciable functional group tolerance.

Язык: Английский

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