Radical NHC Catalysis

ACS Catalysis, Год журнала: 2022, Номер 12(19), С. 11984 - 11999

Опубликована: Сен. 19, 2022

Radical/radical cross-coupling reactions represent an efficient and straightforward approach for the construction of chemical bonds accordingly have drawn increasing attention over past decades. In order to achieve synthetically useful transformations, a persistent radical should be coupled with transient in accordance effect (PRE). However, known radicals outnumber by far types free radicals, which limits widespread application PRE, until today. Thus, development between has been focus, meanwhile transition-metal catalysis successfully implemented artificially prolong lifetimes, allowing their utilization formal radical/radical cross-couplings. Complementary research field recently uncovered that organocatalytically generated NHC-derived ketyl are type catalytically radicals. NHC-catalyzed transformations aldehydes carboxylic acid derivatives enabled disclosure ever-increasing number interesting reactions, different from traditional ionic processes, offering otherwise inaccessible activation modes. These discoveries opened door NHC organocatalysis manipulation reactions. Due its obvious potential synthetic organic chemistry, it is timely provide perspective on this emerging field.

Язык: Английский

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Radical transformations for allene synthesis

Chemical Science, Год журнала: 2022, Номер 13(29), С. 8491 - 8506

Опубликована: Янв. 1, 2022

Allenes are valuable organic molecules that feature unique physical and chemical properties. They not only often found in natural products, but also act as versatile building blocks for the access of complex molecular targets, such pharmaceuticals, functional materials. Therefore, many remarkable elegant methodologies have been established synthesis allenes. Recently, more methods radical allenes developed, clearly emphasizing associated great synthetic values. In this perspective, we will discuss recent important advances

Язык: Английский

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Design principles of the use of alkynes in radical cascades

Nature Reviews Chemistry, Год журнала: 2023, Номер 7(6), С. 405 - 423

Опубликована: Март 28, 2023

Язык: Английский

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Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Сен. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Язык: Английский

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Recent advances in N-heterocyclic carbene (NHC)-catalyzed fluorination and fluoroalkylation

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(7), С. 2112 - 2133

Опубликована: Янв. 1, 2024

Organofluorine compounds are of high value. NHC-catalyzed fluorination and fluoroalkylation have served as powerful versatile vehicles for accessing the related organofluorines. This review focuses on recent developments in this area.

Язык: Английский

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Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Авг. 26, 2022

Abstract The merger of photoredox and transition-metal catalysis has evolved as a robust platform in organic synthesis over the past decade. stereoselective 1,4-functionalization 1,3-enynes, prevalent synthon synthetic chemistry, could afford valuable chiral allene derivatives. However, tremendous efforts have been focused on ionic reaction pathway. radical-involved asymmetric 1,3-enynes remains prominent challenge. Herein, we describe three-component 1,4-dialkylation via dual chromium to provide allenols. This method features readily available starting materials, broad substrate scope, good functional group compatibility, high regioselectivity, simultaneous control axial central chiralities. Mechanistic studies suggest that this proceeds through redox-neutral

Язык: Английский

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Recent advances in three-component radical acylative difunctionalization of unsaturated carbon–carbon bonds

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(18), С. 4488 - 4515

Опубликована: Янв. 1, 2023

This review highlights the recent advances in radical acylated difunctionalization of unsaturated carbon–carbon bonds and focuses on mechanistic insights these transformations.

Язык: Английский

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Remote Radical 1,3-, 1,4-, 1,5-, 1,6- and 1,7-Difunctionalization Reactions

Molecules, Год журнала: 2023, Номер 28(7), С. 3027 - 3027

Опубликована: Март 28, 2023

Radical transformations are powerful in organic synthesis for the construction of molecular scaffolds and introduction functional groups. In radical difunctionalization reactions, radicals first functionalized intermediates can be relocated through resonance, hydrogen atom or group transfer, ring opening. The resulting undertake following paths second functionalization: (1) couple with other groups, (2) oxidize to cations then react nucleophiles, (3) reduce anions electrophiles, (4) metal-complexes. rearrangements provide opportunity 1,3-, 1,4-, 1,5-, 1,6-, 1,7-difunctionalization products. Multiple ways initiate reaction coupling intermediate make reactions good at remote positions. These offer advantages synthetic efficiency, operation simplicity, product diversity.

Язык: Английский

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Synthesis of Trifluoromethyl-Substituted Allenols via Catalytic Trifluoromethylbenzoxylation of 1,3-Enynes

ACS Catalysis, Год журнала: 2023, Номер 13(3), С. 2142 - 2148

Опубликована: Янв. 25, 2023

Allenol has been identified as a versatile building block for organic synthesis, and numerous efforts have made to synthesize apply allenol. However, limited obtain trifluoromethyl-substituted Here, by using readily available 1,3-enyne the starting material, copper-catalyzed trifluoromethylbenzoxylation process was developed efficient synthesis of allenols Togni-II reagent reaction partner. Triple roles reagent, including source trifluoromethyl group, hydroxyl oxidant, were elucidated in this transformation. Moreover, late-stage diversification performed, which revealed application potential preparation various compounds.

Язык: Английский

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Visible light-mediated NHC and photoredox co-catalyzed 1,2-sulfonylacylation of allenesviaacyl and allyl radical cross-coupling

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(4), С. 1047 - 1055

Опубликована: Янв. 1, 2023

Visible light-mediated NHC and photoredox co-catalyzed radical 1,2-sulfonylacylation of allenes via cross-coupling between an allyl NHC-stabilized acyl radical.

Язык: Английский

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