C–H activation

Nature Reviews Methods Primers, Год журнала: 2021, Номер 1(1)

Опубликована: Июнь 17, 2021

Язык: Английский

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Toolbox for Distal C–H Bond Functionalizations in Organic Molecules

Chemical Reviews, Год журнала: 2021, Номер 122(6), С. 5682 - 5841

Опубликована: Окт. 18, 2021

Transition-metal-catalyzed C–H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted take help this methodology plan their synthetic discourses. This paradigm shift helped in development industrial units as well, making synthesis natural products and pharmaceutical drugs step-economical. In vast zone bond activation, functionalization proximal bonds gained utmost popularity. Unlike bonds, distal is more strenuous requires distinctly specialized techniques. review, we compiled various methods adopted functionalize mechanistic insights within each these procedures, scope methodology. With give complete overview expeditious progress made field organic chemistry while also highlighting its pitfalls, thus leaving open for further modifications.

Язык: Английский

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Transition-Metal-Catalyzed, Coordination-Assisted Functionalization of Nonactivated C(sp³)–H Bonds

Chemical Reviews, Год журнала: 2021, Номер 121(24), С. 14957 - 15074

Опубликована: Окт. 29, 2021

Transition-metal-catalyzed, coordination-assisted C(sp3)–H functionalization has revolutionized synthetic planning over the past few decades as use of these directing groups allowed for increased access to many strategic positions in organic molecules. Nonetheless, several challenges remain preeminent, such requirement high temperatures, difficulty removing or converting groups, and, although metals provide some reactivity, employing outside palladium. This review aims give a comprehensive overview coordination-assisted, transition-metal-catalyzed, direct nonactivated bonds by covering literature since 2004 order demonstrate current state-of-the-art methods well limitations. For clarity, this been divided into nine sections transition metal catalyst with subdivisions type bond formation. Synthetic applications and reaction mechanism are discussed where appropriate.

Язык: Английский

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Transition-Metal-Catalyzed C–H Bond Activation for the Formation of C–C Bonds in Complex Molecules

Chemical Reviews, Год журнала: 2023, Номер 123(12), С. 7692 - 7760

Опубликована: Май 10, 2023

Site-predictable and chemoselective C–H bond functionalization reactions offer synthetically powerful strategies for the step-economic diversification of both feedstock fine chemicals. Many transition-metal-catalyzed methods have emerged selective activation bonds. However, challenges regio- chemoselectivity with application to highly complex molecules bearing significant functional group density diversity. As molecular complexity increases within structures risks catalyst intolerance limited applicability grow number groups potentially Lewis basic heteroatoms. Given abundance bonds already diversified such as pharmaceuticals, natural products, materials, design selection reaction conditions tolerant catalysts has proved critical successful direct functionalization. such, innovations formation carbon–carbon been discovered developed overcome these limitations. This review highlights progress made metal-catalyzed C–C forming including alkylation, methylation, arylation, olefination targets.

Язык: Английский

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Stereodynamic Strategies to Induce and Enrich Chirality of Atropisomers at a Late Stage

Chemical Reviews, Год журнала: 2023, Номер 123(17), С. 10641 - 10727

Опубликована: Авг. 28, 2023

Enantiomers, where chirality arises from restricted rotation around a single bond, are atropisomers. Due to the unique nature of origins their chirality, synthetic strategies access these compounds in an enantioselective manner differ those used prepare enantioenriched containing point arising unsymmetrically substituted carbon center. In particular stereodynamic transformations, such as dynamic kinetic resolutions, thermodynamic and deracemizations, which rely on ability racemize or interconvert enantiomers, promising set transformations optically pure late stage sequence. Translation approaches with atropisomers requires expanded toolbox for epimerization/racemization provides opportunity develop new conceptual framework synthesis compounds.

Язык: Английский

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Late-stage functionalization of peptides via a palladium-catalyzed C(sp³)–H activation strategy

Chemical Communications, Год журнала: 2020, Номер 56(90), С. 13950 - 13958

Опубликована: Янв. 1, 2020

Peptides hold great promise in proteomics, diagnostics and drug discovery. While natural peptides continue to be of key importance, chemically modified unnatural have been found show enhanced biological activities improved therapeutic capabilities compared their counterparts. Therefore, the development efficient versatile strategies enable easy access is high demand. In recent years, palladium-catalyzed direct functionalization inert C(sp3)-H bonds has emerged as a powerful straightforward synthetic strategy for late-stage modification peptides. this review, we summarize progress emerging field. For clarity, review organized into three sections according peptide side-chains at β-, γ-, δ-positions.

Язык: Английский

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Late‐Stage Peptide Macrocyclization by Palladium‐Catalyzed Site‐Selective C−H Olefination of Tryptophan

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(34), С. 14686 - 14692

Опубликована: Июнь 8, 2020

Transition-metal-catalyzed C-H activation has shown potential in the functionalization of peptides with expanded structural diversity. Herein, development late-stage peptide macrocyclization methods by palladium-catalyzed site-selective C(sp2 )-H olefination tryptophan residues at C2 and C4 positions is reported. This strategy utilizes backbone as endogenous directing groups provides access to macrocycles unique Trp-alkene crosslinks.

Язык: Английский

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Emerging Organometallic Methods for the Synthesis of C‐Branched (Hetero)aryl, Alkenyl, and Alkyl Glycosides: C−H Functionalization and Dual Photoredox Approaches

Chemistry - A European Journal, Год журнала: 2020, Номер 27(2), С. 491 - 511

Опубликована: Авг. 28, 2020

Abstract Transition‐metal‐catalyzed C−H functionalization and photoredox nickel dual catalysis have emerged as innovative powerful avenues for the synthesis of C‐branched glycosides. These two concepts been recently established provide efficient mild methods accessing a series valuable complex glycosides great interest. Herein, recent developments in aryl/alkenyl/alkyl through these approaches are highlighted.

Язык: Английский

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Peptide Late-Stage Diversifications by Rhodium-Catalyzed Tryptophan C7 Amidation

Chem, Год журнала: 2020, Номер 6(12), С. 3428 - 3439

Опубликована: Ноя. 20, 2020

Язык: Английский

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Stereoselective Synthesis of C‐Vinyl Glycosides via Palladium‐Catalyzed C−H Glycosylation of Alkenes

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(36), С. 19620 - 19625

Опубликована: Июль 6, 2021

C-vinyl glycosides are an important class of carbohydrates and pose a unique synthetic challenge. A new strategy has been developed for stereoselective synthesis via Pd-catalyzed directed C-H glycosylation alkenes with glycosyl chloride donors using easily removable bidentate auxiliary. Both the γ bond allylamines δ homoallyl amine substrates can be glycosylated in high efficiency excellent regio- stereoselectivity. The resulting further converted to variety C-alkyl stereospecificity. These reactions offer broadly applicable method streamline complex from accessible starting materials.

Язык: Английский

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