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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A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry

Chemical Society Reviews, Год журнала: 2018, Номер 47(17), С. 6603 - 6743

Опубликована: Янв. 1, 2018

The present review is devoted to summarizing the recent advances (2015-2017) in field of metal-catalysed group-directed C-H functionalisation. In order clearly showcase molecular diversity that can now be accessed by means directed functionalisation, whole organized following directing groups installed on a substrate. Its aim comprehensive reference work, where specific group easily found, together with transformations which have been carried out it. Hence, primary format this schemes accompanied concise explanatory text, are ordered sections according their chemical structure. feature typical substrates used, products obtained as well required reaction conditions. Importantly, each example commented respect most important positive features and drawbacks, aspects such selectivity, substrate scope, conditions, removal, greenness. targeted readership both experts functionalisation chemistry (to provide overview progress made last years) and, even more so, all organic chemists who want introduce way thinking for design straightforward, efficient step-economic synthetic routes towards molecules interest them. Accordingly, should particular also scientists from industrial R&D sector. overall goal promote application reactions outside research dedicated method development establishing it valuable archetype contemporary R&D, comparable role cross-coupling play date.

Язык: Английский

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Photoredox-Catalyzed C–H Functionalization Reactions

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 1925 - 2016

Опубликована: Сен. 29, 2021

The fields of C–H functionalization and photoredox catalysis have garnered enormous interest utility in the past several decades. Many different scientific disciplines relied on strategies including natural product synthesis, drug discovery, radiolabeling, bioconjugation, materials, fine chemical synthesis. In this Review, we highlight use reactions. We separate review into inorganic/organometallic catalysts organic-based catalytic systems. Further subdivision by reaction class─either sp2 or sp3 functionalization─lends perspective tactical for these methods synthetic applications.

Язык: Английский

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Selective functionalization of methane, ethane, and higher alkanes by cerium photocatalysis

Science, Год журнала: 2018, Номер 361(6403), С. 668 - 672

Опубликована: Июль 26, 2018

With the recent soaring production of natural gas, use methane and other light hydrocarbon feedstocks as starting materials in synthetic transformations is becoming increasingly economically attractive, although it remains chemically challenging. We report development photocatalytic C-H amination, alkylation, arylation methane, ethane, higher alkanes under visible irradiation at ambient temperature. High catalytic efficiency (turnover numbers up to 2900 for 9700 ethane) selectivity were achieved using abundant, inexpensive cerium salts photocatalysts. Ligand-to-metal charge transfer excitation generated alkoxy radicals from simple alcohols that turn acted hydrogen atom catalysts. The mixed-phase gas/liquid reaction was adapted continuous flow, enabling efficient gaseous scalable transformations.

Язык: Английский

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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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Enantioselective C−H Activation with Earth‐Abundant 3d Transition Metals

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(37), С. 12803 - 12818

Опубликована: Май 11, 2019

Molecular syntheses largely rely on time- and labour-intensive prefunctionalization strategies. In contrast, C-H activation represents an increasingly powerful approach that avoids lengthy of prefunctionalized substrates, with great potential for drug discovery, the pharmaceutical industry, material sciences, crop protection, among others. The enantioselective functionalization omnipresent bonds has emerged as a transformative tool step- atom-economical generation chiral molecular complexity. However, this rapidly growing research area remains dominated by noble transition metals, prominently featuring toxic palladium, iridium rhodium catalysts. Indeed, despite significant achievements, use inexpensive sustainable 3d metals in asymmetric activations is still clearly its infancy. Herein, we discuss remarkable recent progress transformations via organometallic base up to April 2019.

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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Alkoxy Radicals See the Light: New Paradigms of Photochemical Synthesis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2429 - 2486

Опубликована: Окт. 6, 2021

Alkoxy radicals are highly reactive species that have long been recognized as versatile intermediates in organic synthesis. However, their development has impeded due to a lack of convenient methods for generation. Thanks advances photoredox catalysis, enabling facile access alkoxy from bench-stable precursors and free alcohols under mild conditions, research interest this field renewed. This review comprehensively summarizes the recent progress radical-mediated transformations visible light irradiation. Elementary steps radical generation either or central reaction development; thus, each section is categorized discussed accordingly. Throughout review, we focused on different mechanisms well impact synthetic utilizations. Notably, catalytic abundant still early stage, providing intriguing opportunities exploit diverse paradigms.

Язык: Английский

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C–H functionalization reactions enabled by hydrogen atom transfer to carbon-centered radicals

Chemical Science, Год журнала: 2020, Номер 11(48), С. 12974 - 12993

Опубликована: Янв. 1, 2020

Intramolecular and intermolecular HAT to C-centered radicals enables selective C–H functionalization of organic molecules.

Язык: Английский

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