Dual‐Catalysed Intermolecular Reductive Coupling of Dienes and Ketones**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(2)

Опубликована: Ноя. 10, 2023

Abstract We report a mild, catalytic method for the intermolecular reductive coupling of feedstock dienes and styrenes with ketones. Our conditions allow concomitant formation cobalt hydride species single‐electron reduction Subsequent selective hydrogen‐atom transfer from generates an allylic radical which can selectively couple persistent radical‐anion ketone. This radical‐radical negates unfavourable steric interactions ionic pathways avoids unstable alkoxy previous olefin‐carbonyl couplings, were limited, as result, to aldehydes. Applications this novel straightforward approach include efficient synthesis drug molecules, key intermediates in site‐selective late‐stage functionalisation.

Язык: Английский

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Electroreductive Cross‐Electrophile Coupling of Aziridines and Aryl Bromides

Chemistry - A European Journal, Год журнала: 2023, Номер 29(36)

Опубликована: Апрель 18, 2023

Herein, a nickela-electrocatalyzed cross-electrophile coupling of readily available aryl aziridines and bromides under mild sustainable electrochemical conditions to access synthetic useful β-arylethylamines is developed. This protocol characterized by its exquisite chemo- regioselectivity, broad substrate scope good functional group compatibility. Mechanistic studies confirmed that the regioselectivity reactivity observed are result electro-induced ring-opening electroreductive generate benzyl radical intermediate as active species. Furthermore, this strategy also enables cross-coupling with CO2 β-amino acids conditions.

Язык: Английский

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Diverse Synthesis of (Thio)ethers and (Thio)esters Using Halodiborylmethane as a Transformable C₁ Building Block

Organic Letters, Год журнала: 2024, Номер 26(33), С. 7010 - 7014

Опубликована: Авг. 8, 2024

The development of effective strategies to forge C–O and C–S bonds in diverse chemical spaces is considerable interest synthetic organic chemistry. Herein we report a versatile approach for the modular synthesis structurally (thio)ethers (thio)esters via homologative coupling α-halodiborylmethane followed by transformation introduced diborylmethyl group. This method accommodates wide array oxygen- sulfur-containing molecules, including biologically active compounds. initial exhibits broad substrate scope, while subsequent diversification moiety enables access various structural motifs through deborylative alkylation, Zweifel olefination, boron-Wittig reaction. protocol efficiently generates diversely functionalized (thio)esters, expanding toolkit accessing relevant scaffolds.

Язык: Английский

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Electrochemical dual α,β-C(sp³)–H functionalization of cyclic N-aryl amines

Green Chemistry, Год журнала: 2023, Номер 25(7), С. 2681 - 2689

Опубликована: Янв. 1, 2023

Herein, a straightforward route for dual α,β-C(sp 3 )–H functionalized cyclic N -aryl amines using combination of electrocatalysis and iron catalysis is disclosed, setting the stage challenging multiple site selective C–H functionalization.

Язык: Английский

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Electrohydrogenation of Nitriles with Amines by Cobalt Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(7)

Опубликована: Дек. 21, 2023

Abstract Catalytic hydrogenation of nitriles represents an efficient and sustainable one‐step synthesis valuable bulk fine chemicals. We report herein a molecular cobalt electrocatalyst for selective hydrogenative coupling with amines using protons as the hydrogen source. The key to success this reductive reaction is use electrocatalytic approach cobalt‐hydride generation through sequence cathodic reduction protonation. As only electrons (e − ) (H + redox equivalent source, general electrohydrogenation protocol showcased by highly straightforward various functionalized structurally diverse amines, well deuterium isotope labeling applications. Mechanistic studies reveal that electrogenerated transfer nitrile process rate‐determining step.

Язык: Английский

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Catalyst-free electrochemical SNAr of electron-rich fluoroarenes using carboxylic acids

eScience, Год журнала: 2024, Номер 4(5), С. 100255 - 100255

Опубликована: Март 15, 2024

Herein, an electrochemically driven catalyst-free nucleophilic aromatic substitution (SNAr) of electron-rich fluoroarenes with carboxylic acids as weak nucleophiles under mild conditions was reported. A series highly valuable ester derivatives were obtained in a direct and rapid way. This transformation features commercially available reagents exceptionally broad substrate scope good functional group tolerance, using cheap abundant electrodes completed within short reaction time. Gram-scale synthesis complex biorelevant compounds ligation further highlighted the potential utility methodology. The mechanistic investigations density theory (DFT) calculations verified feasibility proposed pathway this transformation.

Язык: Английский

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Cobalt‐Catalyzed Wagner–Meerwein Rearrangements with Concomitant Nucleophilic Hydrofluorination

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(35)

Опубликована: Июль 6, 2023

We report a cobalt-catalyzed Wagner-Meerwein rearrangement of gem-disubstituted allylarenes that generates fluoroalkane products with isolated yields up to 84 %. Modification the counteranion N-fluoropyridinium oxidant suggests substrates undergo nucleophilic fluorination during reaction. Subjecting other known metal-mediated hydrofluorination procedures did not lead observable 1,2-aryl migration. Thus, indicating unique ability these conditions generate sufficiently reactive electrophilic intermediate capable promoting this rearrangement.

Язык: Английский

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Electrocatalytic radical-polar crossover hydrofunctionalization of alkenes via cobalt-catalyzed hydrogen atom transfer

Current Opinion in Electrochemistry, Год журнала: 2024, Номер 44, С. 101449 - 101449

Опубликована: Фев. 2, 2024

Язык: Английский

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Electrochemical-induced hydrofunctionalizations of alkenes and alkynes

Chemical Synthesis, Год журнала: 2024, Номер 4(1)

Опубликована: Март 1, 2024

The hydrofunctionalizations of readily available alkenes and alkynes are one the most effective useful routes to afford diverse value-added compounds. Although traditional hydrofunctionalization strategies catalyzed by metal catalysts present convenient approaches, they also accompanied resource consumption environmental crisis. Electrosynthesis, as a renewable sustainable technology, has become cost- atom-efficient synthetic route. In this review, electrochemical-induced summarized presented. each section, electrochemical strategy access hydrogenation other (hydroboration, hydrosilylation, hydroalkylation, hydroalkoxylation, hydrocyanation, hydrocarboxylation, etc. ) products elaborated in detail separately. Finally, current challenges prospects for unsaturated carbon‒carbon (C‒C) bonds discussed briefly.

Язык: Английский

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When transition-metal catalysis meets electrosynthesis: a recent update

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(22), С. 4390 - 4419

Опубликована: Янв. 1, 2024

The merger of organic electrosynthesis with 3d transition-metal catalysis has offered huge opportunities for modern synthesis. This review summarizes the key advancements in this direction published recent two years.

Язык: Английский

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