C–H Activation: Toward Sustainability and Applications

ACS Central Science, Год журнала: 2021, Номер 7(2), С. 245 - 261

Опубликована: Фев. 2, 2021

Since the definition of "12 Principles Green Chemistry" more than 20 years ago, chemists have become increasingly mindful need to conserve natural resources and protect environment through judicious choice synthetic routes materials. The direct activation functionalization C–H bonds, bypassing intermediate functional group installation is, in abstracto, step atom economic, but numerous factors still hinder sustainability large-scale applications. In this Outlook, we highlight research areas seeking overcome challenges activation: pursuit abundant metal catalysts, avoidance static directing groups, replacement oxidants, introduction bioderived solvents. We close by examining progress made subfield aryl borylation from its origins, highly efficient precious Ir-based systems, emerging 3d catalysts. future growth field will depend on industrial uptake, thus urge researchers strive toward sustainable activation.

Язык: Английский

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Strategic evolution in transition metal-catalyzed directed C–H bond activation and future directions

Coordination Chemistry Reviews, Год журнала: 2020, Номер 431, С. 213683 - 213683

Опубликована: Дек. 9, 2020

Язык: Английский

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Recent advances in FeCl3-photocatalyzed organic reactions via hydrogen-atom transfer

Chinese Chemical Letters, Год журнала: 2024, Номер 35(9), С. 109517 - 109517

Опубликована: Янв. 21, 2024

Язык: Английский

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The emergence of the C–H functionalization strategy in medicinal chemistry and drug discovery

Chemical Communications, Год журнала: 2021, Номер 57(83), С. 10842 - 10866

Опубликована: Янв. 1, 2021

Owing to the market competitiveness and urgent societal need, an optimum speed of drug discovery is important criterion for successful implementation. Despite rapid ascent artificial intelligence computational bioanalytical techniques accelerate in big pharma, organic synthesis privileged scaffolds predicted silico vitro vivo studies still considered as rate-limiting step. C-H activation latest technology added into chemist's toolbox construction late-stage modification functional molecules achieve desired chemical physical properties. Particularly, elimination prefunctionalization steps, exceptional group tolerance, complexity-to-diversity oriented synthesis, functionalization medicinal expand space. It has immense potential a library molecules, structural required pharmacological properties such absorption, distribution, metabolism, excretion, toxicology (ADMET) attachment reporters proteome profiling, metabolite etc. preclinical studies. Although heterocycle modification, 18F labelling, methylation, via have been reviewed from synthetic standpoint, general overview these protocols aspects not reviewed. In this feature article, we will discuss recent trends methodologies through activation/annulation cascade; arylation sp2-sp2 sp2-sp3 cross-coupling; borylation/silylation introduce linchpin further manipulation; amination N-heterocycles hydrogen bond acceptors; fluorination/fluoroalkylation tune polarity lipophilicity; methylation: methyl magic discovery; peptide macrocyclization therapeutics biologics; fluorescent labelling radiolabelling bioimaging; bioconjugation biology studies; drug-metabolite biodistribution excretion diversification drug-molecules increase efficacy safety; cutting-edge DNA encoded improved chemistry discovery.

Язык: Английский

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C–H bond functionalization by high-valent cobalt catalysis: current progress, challenges and future perspectives

Chemical Communications, Год журнала: 2021, Номер 57(83), С. 10827 - 10841

Опубликована: Янв. 1, 2021

Over the last decade, high-valent cobalt catalysis has earned a place in spotlight as valuable tool for C-H activation and functionalization. Since discovery of its unique reactivity, more attention been directed towards utilization an alternative to noble metal catalysts. In particular, Cp*Co(III) complexes, well simple Co(II) Co(III) salts combination with bidentate chelation assistance, have extensively used development novel transformations. this review, we demonstrated existing trends functionalization methodology using highlighted main challenges overcome, perspective directions, which need be further developed future.

Язык: Английский

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Orthogonal Access to α‐/β‐Branched/Linear Aliphatic Amines by Catalyst‐Tuned Regiodivergent Hydroalkylations

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(34)

Опубликована: Июнь 21, 2022

Abstract Linear, α‐branched, and β‐branched aliphatic amines are widespread in pharmaceuticals, agrochemicals, fine chemicals. Thus, the development of direct efficient methods to these structures a tunable manner is highly desirable yet challenging. Herein, catalyst‐controlled synthesis linear from Ni/Co‐catalyzed regio‐ site‐selective hydroalkylations alkenyl with alkyl halides developed. This catalytic protocol features reliable prediction control coupling position alkylation provide orthogonal access identical starting materials. platform unlocks reactivity selectivity nickel hydride cobalt chemistry catalytically repurpose three types under mild conditions.

Язык: Английский

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Tandem Reactions involving 1,4‐Palladium Migrations

Chemistry - An Asian Journal, Год журнала: 2022, Номер 17(15)

Опубликована: Июнь 6, 2022

Abstract Transition‐metal‐catalyzed tandem reactions have become a mainstay in organic chemistry owing to their high atom‐ and step‐economies. Metal‐migration‐based allow the engagement of simple starting materials for incorporating functional groups into certain positions constructing complex scaffolds, which provide novel means that are complementary traditional cross‐coupling or C−H activation processes. In light broad utility 1,4‐Pd migration reaction, this paper reviews its progress past two decades, summarizing process classifying it based on insertion, elimination, transmetalation, bond activation. Special emphasis is placed driving force Pd different mechanisms. Moreover, review also attempts summarize common strategies improving regio‐ site‐selectivities process.

Язык: Английский

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The green chemistry paradigm in modern organic synthesis

Russian Chemical Reviews, Год журнала: 2023, Номер 92(12), С. RCR5104 - RCR5104

Опубликована: Дек. 1, 2023

After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.

Язык: Английский

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Condition-Controlled Selective Synthesis of Pyranone-Tethered Indazoles or Carbazoles through the Cascade Reactions of N-Nitrosoanilines with Iodonium Ylides

Organic Letters, Год журнала: 2023, Номер 25(24), С. 4422 - 4428

Опубликована: Июнь 8, 2023

Presented herein is a condition-controlled selective synthesis of pyranone-tethered indazoles or carbazole derivatives via the cascade reactions N-nitrosoanilines with iodonium ylides. Mechanistically, formation former involves an unprecedented process including nitroso group-directed C(sp2)–H bond alkylation N-nitrosoaniline ylide followed by intramolecular C-nucleophilic addition to moiety, solvent-assisted cyclohexanedione ring opening, and transesterification/annulation. On contrary, latter initial annulation denitrosation. These developed protocols feature easily controllable selectivity, mild reaction conditions, clean sustainable oxidant (air), valuable products that are structurally diverse. In addition, utility was showcased their facile diverse transformations into synthetically biologically interesting compounds.

Язык: Английский

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A Guide to Directing Group Removal: 8‐Aminoquinoline

Chemistry - A European Journal, Год журнала: 2021, Номер 27(33), С. 8411 - 8436

Опубликована: Фев. 10, 2021

The use of directing groups allows high levels selectivity to be achieved in transition metal-catalyzed transformations. Efficient removal these auxiliaries after successful functionalization, however, can very challenging. This review provides a critical overview strategies used for Daugulis' 8-aminoquinoline (2005-2020), one the most widely N,N-bidentate groups. limitations are discussed and alternative approaches suggested challenging substrates. Our aim is provide comprehensive end-users' guide chemists academia industry who want harness synthetic power groups-and able remove them from their final products.

Язык: Английский

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