Electrochemical Aziridination of Internal Alkenes with Primary Amines

Ošeka, Maksim; Laudadio, Gabriele; Leest, Nicolaas P. van; Dyga, Marco; Bartolomeu, Aloísio de Andrade; Gooßen, Lukas J.; Bruin, Bas de; Oliveira, Kléber T. de; Noël, Timothy

doi:10.1016/j.chempr.2020.12.002

Cited by 71 publications

(50 citation statements)

References 67 publications

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“…[29][30][31] This knowledge and the previous experience helped us to develop a convenient continuous-flow methodology for the electrochemical hydroxylation of electronrich aromatic compounds by the use of trifluoroacetic acid as the oxygen source. [32][33][34][35] With this procedure we successfully demonstrate a scale-up experiment as well (Scheme 1, C).…”

Section: Introductionmentioning

confidence: 85%

“…High electrode surface‐to‐volume ratio and effective mixing significantly reduce the reaction time (typically 5 min in flow vs. overnight in batch), which helps to prevent degradation of sensitive products under electrochemical conditions and increases the reaction selectivity [29–31] . This knowledge and the previous experience helped us to develop a convenient continuous‐flow methodology for the electrochemical hydroxylation of electron‐rich aromatic compounds by the use of trifluoroacetic acid as the oxygen source [32–35] . With this procedure we successfully demonstrate a scale‐up experiment as well (Scheme 1, C).…”

Section: Introductionmentioning

confidence: 86%

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Electrochemical Hydroxylation of Electron‐Rich Arenes in Continuous Flow

et al. 2022

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Dedicated to Laura Ošeka, who was born during the preparation of the manuscript for this article and helped to write it.Electrochemical hydroxylation of arenes by trifluoroacetic acid provides a straightforward access to aryl oxygen compounds under the mild and environmental benign reaction conditions. Harmful and pollutant stoichiometric amounts of oxidation reagents and the use of metal-catalysts can be avoided. Herein, we present a novel method for the synthesis of hydroxylated products from electron-rich arenes that was achieved by the implementation of a continuous-flow setup. The continuous nature of the process allowed to fine-tune the reactions conditions in order to prevent the decomposition of the sensitive products expanding the reaction scope beyond electron-poor and neutral arenes that were previously reported in the batch processes. Thus, synthetically valuable hydroxylated arenes were obtained in good yields with the residence time just over a minute. In order to demonstrate the reliability and the efficiency of the electrochemical flow setup, a scale up experiment was also performed.

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Section: Introductionmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 86%

Electrochemical Hydroxylation of Electron‐Rich Arenes in Continuous Flow

et al. 2022

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“…To distinguish the heterogeneous catalyst system from its homogeneous precursors, a few control experiments were carried out. The reaction did not take place when no catalyst was used, and employing Co(OAc)2•4H2O alone or its physical mixture with 1,10phenanthroline both failed to generate product 3a, moreover, the non-pyrolyzed Co-phen(2)@C also did not work for this transformation (entries [8][9][10][11]. These interesting results triggered us to identify the inherent composition of the nano-cobalt catalyst, and to apply this nano-cobalt system for broader aziridine synthesis.…”

Section: Scheme 3 Preparation Of Nano-cobalt Catalystmentioning

confidence: 99%

Chemo-selective Aziridination and Oxyamination of Alkenes with Nano-cobalt catalyst

Xue

Chen

Yang

et al. 2022

Preprint

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Aziridine synthesis from readily available alkene has been a long-standing point of interest for organic chemists, owing to the widely existence in bioactive compounds and plentiful synthetic derivatizations of aziridines. Compared with using iminoiodinane or azide as the nitrogen source, the seeking for catalytic systems employing novel nitrogen transfer reagent under external oxidant-free conditions are the cutting-edge techniques in this field. Herein, a pioneering nano-cobalt catalyzed chemo-selective aziridination/oxyamination reaction from alkene and hydroxylamine is developed, this system proceeds without external oxidant and exhibits mild, efficient, atom-economic and recyclable characters. Late-stage aziridinations of drug-derived alkenes and diversified synthetic transformation of the aziridine product further expands the utility of this method. Moreover, this novel methodology represents a rare example of alkene difunctionalization under nano-catalyst, which bridges the gap between homo- and heterogeneous catalysis. Moreover, the full characterizations of the nano-cobalt catalyst and mechanistic studies including deuterium-labeled experiment and Hammet analysis were conducted, while a reasonable mechanism was also suggested accordingly.

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“…Most recently, ammonia was successfully utilized to build aziridination via this pattern. [16] The intramolecular [17] and intermolecular [18] electrochemical C -H activation was also adopted in the aziridination reactions. With these precedents, however, the aziridination of electron-deficient alkene is only marginally explored by Yudin group, [13a] which required a dividing cell (Scheme 1,b).…”

Section: Introductionmentioning

confidence: 99%

Aryl-Iodide-Mediated Electrochemical Aziridination of Electron-Deficient Alkenes

Liu¹,

Dai²,

Xu³

2021

Chinese Journal of Organic Chemistry

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A protocol of electrochemical aziridination of electron-deficient alkenes was reported using phthalhydrazide as nitrogen source. The reaction could be conducted in undivided cell, and the ArI is essential to achieve the transformation. Hypervalent-iodine-stablized nitrene and acetyl hydroxyhydrazine were suggested as the in-situ generated nitrogen source for the stepwise aziridination. This protocol can be applied to the azirdination of α,β-unsaturated esters, amides, nitrile and ketones to give a series N-containing molecules.

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Electrochemical Aziridination of Internal Alkenes with Primary Amines

Cited by 71 publications

References 67 publications

Electrochemical Hydroxylation of Electron‐Rich Arenes in Continuous Flow

Electrochemical Hydroxylation of Electron‐Rich Arenes in Continuous Flow

Chemo-selective Aziridination and Oxyamination of Alkenes with Nano-cobalt catalyst

Aryl-Iodide-Mediated Electrochemical Aziridination of Electron-Deficient Alkenes

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