Electrocatalysis as an enabling technology for organic synthesis

Chemical Society Reviews, Год журнала: 2021, Номер 50(14), С. 7941 - 8002

Опубликована: Янв. 1, 2021

Electrochemistry has recently gained increased attention as a versatile strategy for achieving challenging transformations at the forefront of synthetic organic chemistry. Electrochemistry's unique ability to generate highly reactive radical and ion intermediates in controlled fashion under mild conditions inspired development number new electrochemical methodologies preparation valuable chemical motifs. Particularly, recent developments electrosynthesis have featured an use redox-active electrocatalysts further enhance control over selective formation downstream reactivity these intermediates. Furthermore, electrocatalytic mediators enable proceed manner that is mechanistically distinct from purely methods, allowing subversion kinetic thermodynamic obstacles encountered conventional synthesis. This review highlights key innovations within past decade area electrocatalysis, with emphasis on mechanisms catalyst design principles underpinning advancements. A host oxidative reductive are discussed grouped according classification transformation nature electrocatalyst.

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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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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Radical C(sp3)–H functionalization and cross-coupling reactions

Nature Reviews Chemistry, Год журнала: 2022, Номер 6(6), С. 405 - 427

Опубликована: Май 17, 2022

Язык: Английский

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Electrochemical generation of nitrogen-centered radicals for organic synthesis

Green Synthesis and Catalysis, Год журнала: 2021, Номер 2(2), С. 165 - 178

Опубликована: Март 29, 2021

There is a resurgence of interests in organic electrochemistry, which generally accepted as green synthetic tool. In this context, many electrochemical methods have been developed the past decade to access various nitrogen-centered radicals (NCRs) from readily available precursors controlled fashion, enabling rapid development NCR-mediated new reactions for construction nitrogen-containing compounds. review, recent advances chemistry electrochemically generated NCRs are critically highlighted, based on strategies their formation and types NCRs. Focus put mechanism generation different applications.

Язык: Английский

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Electrochemical Late-Stage Functionalization

Chemical Reviews, Год журнала: 2023, Номер 123(19), С. 11269 - 11335

Опубликована: Сен. 26, 2023

Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical biological activities. LSF can thus greatly accelerate development medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical synthesis has emerged as an environmentally friendly platform transformation organic compounds. Over past decade, electrochemical late-stage (eLSF) gained major momentum, which is summarized herein up to February 2023.

Язык: Английский

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New Strategies for the Synthesis of Aliphatic Azides

Chemical Reviews, Год журнала: 2021, Номер 121(7), С. 4253 - 4307

Опубликована: Фев. 26, 2021

Aliphatic azides are a versatile class of compounds found in variety biologically active pharmaceuticals. These also recognized as useful precursors for the synthesis range nitrogen-based scaffolds therapeutic drugs, compounds, and functional materials. In light growing importance aliphatic both chemical biological sciences, vast array synthetic strategies preparation structurally diverse have been developed over past decades. However, to date, this topic has not subject dedicated review. This review aims provide concise overview modern access that emerged since 2010. The discussed azidation reactions include (a) C–C multiple bonds, (b) C–H (c) direct transformation vinyl into other azides, (d) miscellaneous azides. We critically discuss outcomes generality uniqueness different mechanistic rationale each selected reactions. challenges potential opportunities outlined.

Язык: Английский

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Exploring Electrochemical C(sp³)–H Oxidation for the Late-Stage Methylation of Complex Molecules

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(3), С. 1187 - 1197

Опубликована: Янв. 11, 2022

The "magic methyl" effect, a dramatic boost in the potency of biologically active compounds from incorporation single methyl group, provides simple yet powerful strategy employed by medicinal chemists drug discovery process. Despite significant advances, methodologies that enable selective C(sp3)–H methylation structurally complex agents remain very limited. In this work, we disclose modular, efficient, and for α-methylation protected amines (i.e., amides, carbamates, sulfonamides) means electrochemical oxidation. Mechanistic analysis guided our development an improved protocol on basis classic Shono oxidation reaction, which features broad reaction scope, high functional group compatibility, operational simplicity. Importantly, system is amenable to late-stage functionalization targets containing basic nitrogen groups are prevalent medicinally agents. When combined with organozinc-mediated C–C bond formation, enabled direct myriad amine derivatives including those have previously been explored effect. This synthesis thus circumvents multistep de novo currently necessary access such has potential accelerate efforts.

Язык: Английский

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Electronic control over site-selectivity in hydrogen atom transfer (HAT) based C(sp³)–H functionalization promoted by electrophilic reagents

Chemical Society Reviews, Год журнала: 2022, Номер 51(6), С. 2171 - 2223

Опубликована: Янв. 1, 2022

Leveraging on electronic effects in both the substrate and HAT reagent, site-selectivity can be implemented C(sp 3 )–H bond functionalization.

Язык: Английский

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The interplay of polar effects in controlling the selectivity of radical reactions

Nature Synthesis, Год журнала: 2022, Номер 1(9), С. 682 - 695

Опубликована: Авг. 1, 2022

Язык: Английский

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