A synthetic chemist's guide to electroanalytical tools for studying reaction mechanisms

Chemical Science, Год журнала: 2019, Номер 10(26), С. 6404 - 6422

Опубликована: Янв. 1, 2019

A range of electroanalytical tools can be applied to studying redox reactions, probing key mechanistic questions in synthetic chemistry.

Язык: Английский

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New Redox Strategies in Organic Synthesis by Means of Electrochemistry and Photochemistry

ACS Central Science, Год журнала: 2020, Номер 6(8), С. 1317 - 1340

Опубликована: Июль 16, 2020

As the breadth of radical chemistry grows, new means to promote and regulate single-electron redox activities play increasingly important roles in driving modern synthetic innovation. In this regard, photochemistry electrochemistry-both considered as niche fields for decades-have seen an explosive renewal interest recent years gradually have become a cornerstone organic chemistry. Outlook article, we examine current state-of-the-art areas electrochemistry photochemistry, well nascent area electrophotochemistry. These techniques employ external stimuli activate molecules imbue privileged control reaction progress selectivity that is challenging traditional chemical methods. Thus, they provide alternative entries known reactive intermediates enable distinct strategies were previously unimaginable. Of many hallmarks, electro- are often classified "green" technologies, promoting reactions under mild conditions without necessity potent wasteful oxidants reductants. This reviews most growth these with special emphasis on conceptual advances given rise enhanced accessibility tools trade.

Язык: Английский

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Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2487 - 2649

Опубликована: Ноя. 9, 2021

Redox processes are at the heart of synthetic methods that rely on either electrochemistry or photoredox catalysis, but how do and catalysis compare? Both approaches provide access to high energy intermediates (e.g., radicals) enable bond formations not constrained by rules ionic 2 electron (e) mechanisms. Instead, they 1e mechanisms capable bypassing electronic steric limitations protecting group requirements, thus enabling chemists disconnect molecules in new different ways. However, while providing similar intermediates, differ several physical chemistry principles. Understanding those differences can be key designing transformations forging disconnections. This review aims highlight these similarities between comparing their underlying principles describing impact electrochemical photochemical methods.

Язык: Английский

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Photochemical and Electrochemical Applications of Proton-Coupled Electron Transfer in Organic Synthesis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2017 - 2291

Опубликована: Ноя. 23, 2021

We present here a review of the photochemical and electrochemical applications multi-site proton-coupled electron transfer (MS-PCET) in organic synthesis. MS-PCETs are redox mechanisms which both an proton exchanged together, often concerted elementary step. As such, MS-PCET can function as non-classical mechanism for homolytic bond activation, providing opportunities to generate synthetically useful free radical intermediates directly from wide variety common functional groups. introduction practitioner’s guide reaction design, with emphasis on unique energetic selectivity features that characteristic this class. then chapters oxidative N–H, O–H, S–H, C–H homolysis methods, generation corresponding neutral species. Then, reductive PCET activations involving carbonyl, imine, other X═Y π-systems, heteroarenes, where ketyl, α-amino, heteroarene-derived radicals be generated. Finally, we asymmetric catalysis materials device applications. Within each chapter, subdivide by group undergoing homolysis, thereafter type transformation being promoted. Methods published prior end December 2020 presented.

Язык: Английский

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Dirhodium tetracarboxylates as catalysts for selective intermolecular C–H functionalization

Nature Reviews Chemistry, Год журнала: 2019, Номер 3(6), С. 347 - 360

Опубликована: Май 7, 2019

Язык: Английский

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Photoinduced intermolecular hydrogen atom transfer reactions in organic synthesis

Chem Catalysis, Год журнала: 2021, Номер 1(3), С. 523 - 598

Опубликована: Май 24, 2021

Язык: Английский

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Advances on the Merger of Electrochemistry and Transition Metal Catalysis for Organic Synthesis

Chemical Reviews, Год журнала: 2021, Номер 122(3), С. 3180 - 3218

Опубликована: Ноя. 19, 2021

Synthetic organic electrosynthesis has grown in the past few decades by achieving many valuable transformations for synthetic chemists. Although electrocatalysis been popular improving selectivity and efficiency a wide variety of energy-related applications, last two decades, there much interest to develop conceptually novel transformations, selective functionalization, sustainable reactions. This review discusses recent advances combination electrochemistry homogeneous transition-metal catalysis synthesis. The enabling mechanistic studies are presented alongside advantages as well future directions address challenges metal-catalyzed electrosynthesis.

Язык: Английский

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Recent advances in organic electrosynthesis employing transition metal complexes as electrocatalysts

Science Bulletin, Год журнала: 2021, Номер 66(23), С. 2412 - 2429

Опубликована: Июль 13, 2021

Язык: Английский

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Making electrochemistry easily accessible to the synthetic chemist

Green Chemistry, Год журнала: 2020, Номер 22(11), С. 3358 - 3375

Опубликована: Янв. 1, 2020

This tutorial bridges an important knowledge gap by providing easily accessible introduction that enables synthetic chemists to explore electrochemistry.

Язык: Английский

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Manganese-Catalyzed Oxidative Azidation of C(sp³)–H Bonds under Electrophotocatalytic Conditions

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(41), С. 17693 - 17702

Опубликована: Сен. 17, 2020

The selective installation of azide groups into C(sp3)-H bonds is a priority research topic in organic synthesis, particularly pharmaceutical discovery and late-stage diversification. Herein, we demonstrate generalized manganese-catalyzed oxidative azidation methodology using nucleophilic NaN3 as an source under electrophotocatalytic conditions. This approach allows us to perform the reaction without necessity adding excess substrate successfully avoiding use stoichiometric chemical oxidants such iodine(III) reagent or NFSI. A series tertiary secondary benzylic C(sp3)-H, aliphatic drug-molecule-based substrates are well tolerated our protocol. simultaneous gram-scale synthesis ease transformation amine collectively advocate for potential application preparative synthesis. Good reactivity bond selectivity incorporate nitrogen-based functionality at alkyl group also provide opportunities manipulate numerous medicinal candidates. We anticipate synthetic protocol, consisting metal catalysis, electrochemistry, photochemistry, would new sustainable option execute challenging transformations.

Язык: Английский

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