3d Transition Metals for C–H Activation

Chemical Reviews, Год журнала: 2018, Номер 119(4), С. 2192 - 2452

Опубликована: Ноя. 27, 2018

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these functionalizations required precious 4d or 5d transition metal catalysts. Given cost-effective sustainable nature earth-abundant first row metals, development less toxic, inexpensive 3d catalysts gained considerable recent momentum a significantly more environmentally-benign economically-attractive alternative. Herein, we provide comprehensive overview on until summer 2018.

Язык: Английский

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Electrochemical strategies for C–H functionalization and C–N bond formation

Chemical Society Reviews, Год журнала: 2018, Номер 47(15), С. 5786 - 5865

Опубликована: Янв. 1, 2018

This review provides an overview of the use electrochemistry as appealing platform for expediting carbon–hydrogen functionalization and carbon–nitrogen bond formation.

Язык: Английский

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Bidentate Directing Groups: An Efficient Tool in C–H Bond Functionalization Chemistry for the Expedient Construction of C–C Bonds

Chemical Reviews, Год журнала: 2020, Номер 120(3), С. 1788 - 1887

Опубликована: Янв. 6, 2020

During the past decades, synthetic organic chemistry discovered that directing group assisted C–H activation is a key tool for expedient and siteselective construction of C–C bonds. Among various strategies, bidentate groups are now recognized as one most efficient devices selective functionalization certain positions due to fact its metal center permits fine, tunable, reversible coordination. The family permit types assistance be achieved, such N,N-dentate, N,O-dentate, N,S-dentate auxiliaries, which categorized based on coordination site. In this review, we broadly discuss bond reactions formation bonds with aid groups.

Язык: Английский

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Recent Advances in Oxidative R¹-H/R²-H Cross-Coupling with Hydrogen Evolution via Photo-/Electrochemistry

Chemical Reviews, Год журнала: 2019, Номер 119(12), С. 6769 - 6787

Опубликована: Май 10, 2019

Photo-/electrochemical catalyzed oxidative R1-H/R2-H cross-coupling with hydrogen evolution has become an increasingly important issue for molecular synthesis. The dream of construction C-C/C-X bonds from readily available C-H/X-H release H2 can be facilely achieved without external chemical oxidants, providing a greener model bond formation. Given the great influence these reactions in organic chemistry, we give summary state art via photo/electrochemistry, and hope this review will stimulate development synthetic strategy near future.

Язык: Английский

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Electrochemical Oxidative Cross-Coupling with Hydrogen Evolution Reactions

Accounts of Chemical Research, Год журнала: 2019, Номер 52(12), С. 3309 - 3324

Опубликована: Ноя. 27, 2019

Oxidative cross-coupling has proved to be one of the most straightforward strategies for forming carbon-carbon and carbon-heteroatom bonds from easily available precursors. Over past two decades, tremendous efforts have been devoted in this field significant advances achieved. However, order remove surplus electrons substrates chemical formation, stoichiometric oxidants are usually needed. Along with development modern sustainable chemistry, considerable perform oxidative reactions under external-oxidant-free conditions. Electrochemical synthesis is a powerful environmentally benign approach, which can not only achieve cross-couplings conditions, but also release valuable hydrogen gas during bond formation. Recently, electrochemical evolution significantly explored. This Account presents our recent toward reactions. (1) We explored thiols/thiophenols arenes, heteroarenes, alkenes C-S (2) Using strategy C-H/N-H evolution, we successfully realized C-H amination phenols, anilines, imidazopyridines, even ethers. (3) Employing halide salts as green halogenating reagents, developed clean halogenation protocol oxidation To address limitation that reaction had carry out aqueous solvent, an alternative method uses CBr4, CHBr3, CH2Br2, CCl3Br, CCl4 reagents mixture acetonitrile methanol cosolvent. (4) approach constructing C-O well-developed manner. (5) Under mild C(sp2)-H C(sp3)-H phosphonylation modest high yields. (6) achieved S-H/S-H By anodic instead oxidants, overoxidation thiols thiophenols was well avoided. (7) The methods structurally diverse heterocyclic compounds were via annulations. (8) applied difunctionalization multiple step, such C-S/C-O bonds, C-S/C-N C-Se/C-O C-Se/C-N bonds. hope studies will stimulate research interest chemists pave way discovery more

Язык: Английский

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Electrocatalytic C–H Activation

ACS Catalysis, Год журнала: 2018, Номер 8(8), С. 7086 - 7103

Опубликована: Июнь 18, 2018

C–H activation has emerged as a transformative tool in molecular synthesis, but until recently oxidative activations have largely involved the use of stoichiometric amounts expensive and toxic metal oxidants, compromising overall sustainable nature chemistry. In sharp contrast, electrochemical been identified more efficient strategy that exploits storable electricity place byproduct-generating chemical reagents. Thus, transition-metal catalysts were shown to enable versatile reactions manner. While palladium catalysis set stage for C(sp2)–H C(sp3)–H functionalizations by N-containing directing groups, rhodium ruthenium allowed weakly coordinating amides acids. contrast these precious 4d transition metals, recent year witnessed emergence cobalt oxygenations, nitrogenations, C–C-forming [4+2] alkyne annulations. Thereby, silver(I) oxidants was prevented, improving environmentally benign catalysis. Herein, we summarize major advances organometallic otherwise inert bonds electrocatalysis through May 2018.

Язык: Английский

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Late-stage C–H functionalization offers new opportunities in drug discovery

Nature Reviews Chemistry, Год журнала: 2021, Номер 5(8), С. 522 - 545

Опубликована: Июль 13, 2021

Язык: Английский

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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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Organic Electrochemistry: Molecular Syntheses with Potential

ACS Central Science, Год журнала: 2021, Номер 7(3), С. 415 - 431

Опубликована: Март 9, 2021

Efficient and selective molecular syntheses are paramount to

Язык: Английский

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Recent Advances in C–H Functionalization Using Electrochemical Transition Metal Catalysis

ACS Catalysis, Год журнала: 2018, Номер 8(8), С. 7179 - 7189

Опубликована: Июнь 19, 2018

Electrochemical transition metal catalysis is a powerful strategy for organic synthesis because it obviates the use of stoichiometric chemical oxidants and reductants. C–H bond functionalization offers variety useful conversions simple ubiquitous molecules into diverse functional groups in single synthetic operation. This review summarizes recent progress merging electrochemistry with metal-catalyzed functionalization, specifically C–C, C–X (halogen), C–O, C–P, C–N formation.

Язык: Английский

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