Direct synthesis of N-arylamides via the coupling of aryl diazonium tetrafluoroborates and nitriles under transition-metal-free conditions

Xiong, Biquan; Wang, Gang; Xiong, Tao; Wan, Liming; Zhou, Congshan; Liu, Yu; Zhang, Panliang; Yang, Changan; Tang, Kewen

doi:10.1016/j.tetlet.2018.07.014

Cited by 9 publications

(4 citation statements)

References 54 publications

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“…Once the initiation happens, the aryl radical can undergo a radical cascade reaction after attacking the terminal carbon of a styrene molecule and generating the benzylic radical species 7. The possibility of a competing chain propagation 60,61 from the benzylic radical to the diazonium salts is also feasible, which could contribute to the overall reaction yield without requiring the involvement of a catalyst. However, the control reactions in the absence of the PLY catalyst show only 15% conversion to the product as compared to the optimized conditions rendering 89% product formation (entries 13 and 1, Table 1).…”

Section: Acs Catalysismentioning

confidence: 99%

Tuning Redox States of Phenalenyl-Based Molecules by Consecutive Reduction toward Transition Metal-Free Heck-Type C–C Cross-Coupling

Banik

Mandal

2022

ACS Catal.

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Phenalenyl-based molecules can switch their redox states on successive addition of electrons from a cation to a radical to an anion. Utilizing this phenomenal ability, we have designed the first example where all three redox states have been utilized to design a Heck-type coupling reaction. In this work, we have developed a protocol where a phenalenyl moiety tunes its redox states and acts as a catalyst in Matsuda−Heck-type and Mizoroki−Heck-type coupling reactions. A wide range of substrate scopes was successfully achieved in both processes under ambient reaction conditions. Moreover, the characterization of active catalysts for both Heck-type couplings was accomplished with the help of different spectroscopic techniques. The control experiments unveiled that these catalytic processes follow a radical mechanism, and several key radical intermediates have been arrested and characterized. It was realized that the catalytic reactions are selective toward the use of mono-and doubly reduced phenalenyl species. This study implies that tuning the energy of the frontier orbital (singly occupied molecular orbital (SOMO) or highest occupied molecular orbital (HOMO)) of the reduced phenalenyl moiety plays a key role in accomplishing these reactions.

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Section: Acs Catalysismentioning

confidence: 99%

Tuning Redox States of Phenalenyl-Based Molecules by Consecutive Reduction toward Transition Metal-Free Heck-Type C–C Cross-Coupling

Banik

Mandal

2022

ACS Catal.

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“…At the same time,wedetected the formation of p-acetotoluidide (5a), which was generated by cross-coupling between aryl diazonium salt and CH 3 CN. [14] When the cathode potential was adjusted to À0.3 V, both 3aa and 5a were detected ( Table 5, entry 2). They ield of desired product increased because p-acetotoluidide (5a)was basically suppressed when the cathodic voltage was set at À0.6 Vo rÀ1.0 V( Table 5, entries 3a nd 4).…”

Section: Communicationsmentioning

confidence: 99%

Electrochemical Arylation of Electron‐Deficient Arenes through Reductive Activation

et al. 2019

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An electrochemical method has been developed to achieve arylation of electron‐deficient arenes through reductive activation. Various electron‐deficient arenes and aryldiazonium tetrafluoroborates are amenable to this transformation within the conditions of an undivided cell, providing the desired products in up to 92 % yield. Instead of preparing diazonium reagents, these reactions can begin from anilines, and they can be carried out in one pot. Electron paramagnetic resonance studies indicate that cathodic reduction of quinoxaline occurs using the transformation. Moreover, cyclic voltammetry indicates that both quinoxaline and aryl diazonium salt have relatively low reduction potentials, which suggests they can be activated through reduction during the reaction.

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“…N ‐arylamides can be obtained via the coupling of aryl diazonium tetrafluoroborates [6b] and nitriles (Scheme 1, ex. 1), or via copper‐catalyzed amidation of diaryliodonium salts [6a] or aryl halides [6d] with nitriles (Scheme 1, ex.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Approach to Amide Bond Formation

Strekalova,

Kononov,

Morozov

et al. 2023

Adv Synth Catal

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Electrochemical amidation of the C(sp2)−H and C(sp3)−H bonds of broad spectrum of arenes toward the direct synthesis of anilides and N‐benzylamides under mild conditions (room temperature, ambient pressure) in the absence of metal catalyst and external oxidizing agents using nitriles RCN (R=Me, Et) as amide source is described. This electrochemical approach features moderate to high yields, a broad scope of arenes with different functional groups and is amenable to gram scale synthesis. The key role of the hydroxyl radical as inductor generated during the oxidation of water and fixed by a spin trap in EPR experiment has been established.

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Direct synthesis of N-arylamides via the coupling of aryl diazonium tetrafluoroborates and nitriles under transition-metal-free conditions

Cited by 9 publications

References 54 publications

Tuning Redox States of Phenalenyl-Based Molecules by Consecutive Reduction toward Transition Metal-Free Heck-Type C–C Cross-Coupling

Tuning Redox States of Phenalenyl-Based Molecules by Consecutive Reduction toward Transition Metal-Free Heck-Type C–C Cross-Coupling

Electrochemical Arylation of Electron‐Deficient Arenes through Reductive Activation

Electrochemical Approach to Amide Bond Formation

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