Direct electrochemical synthesis of arenesulfonyl fluorides from nitroarenes: a dramatic ionic liquid effect

Kong, Xianqiang; Liu, Qianwen; Chen, Yiyi; Wang, Wei; Chen, Hong-Fa; Wang, Wenjie; Zhang, Shuangquan; Chen, Xiaohui; Cao, Zhong-Yan

doi:10.1039/d3gc04528e

Cited by 14 publications

(7 citation statements)

References 81 publications

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“…The typical methods used to construct fluorosulfonyl moieties include the nucleophilic substitution of sulfonyl chlorides or its surrogates by fluorides, and direct electrophilic fluorination of sulfinate salts or sulfonyl radical intermediates (Figure B) . Thus, we envisioned that the development of a novel metal catalyst that can assemble a fluorosulfonyl group via a transition metal-catalyzed FAT process to sulfonyl radical intermediates will undoubtedly expand the types of methodologies for synthesizing sulfonyl fluorides.…”

Section: Introductionmentioning

confidence: 99%

Copper-Mediated Radical Fluorine-Atom Transfer to Sulfonyl Radical: A Dramatic 4-Methoxypyridine 1-Oxide Ligand Effect

Zhang,

Sun,

et al. 2024

ACS Catal.

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Although the transition metal-catalyzed radical fluorine atom transfer (FAT) strategy has emerged as a powerful tool for the construction of C–F bonds, to our knowledge, this approach has rarely been applied to the formation of S–F bonds. Here, we report that 4-methoxypyridine 1-oxide can serve as an inexpensive and simple yet effective ligand and thus promote the transformation of the copper-mediated challengeable radical FAT to sulfonyl radicals, paving the way for the assembly of an FSO2 group. Based on this concept, three Cu(I)-catalyzed protocols involving site-selective intra- and intermolecular fluorosulfonylation of inert C(sp3)–H bonds and 1,2-aminofluorosulfonylation of inactivated alkenes have been developed, enabling the preparation of C(sp3)-rich aliphatic sulfonyl fluorides that cannot be easily synthesized by known methods. These practical and operationally simple methods result in high functional group tolerance under mild conditions and can be applied to the modification of bioactive derivatives and preparation of highly valued molecules. Detailed mechanistic studies indicate the unique role of the 4-methoxypyridine 1-oxide ligand in facilitating the formation of such rare radical FATs via an outer-sphere pathway.

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Section: Introductionmentioning

confidence: 99%

Copper-Mediated Radical Fluorine-Atom Transfer to Sulfonyl Radical: A Dramatic 4-Methoxypyridine 1-Oxide Ligand Effect

Zhang,

Sun,

et al. 2024

ACS Catal.

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“…1a ). These structurally valuable frameworks offer distinct advantages, including enhanced solubility, improved pharmacokinetics, and increased bioavailability, 2 capturing significant attention from both industry and academia. Despite their importance, the aromatic driving force directs the construction toward five-membered heterocyclic aromatic compounds like triazole, imidazole, thiazole, thiophene, and furan.…”

Section: Introductionmentioning

confidence: 99%

CoH-catalyzed asymmetric remote hydroalkylation of heterocyclic alkenes: a rapid approach to chiral five-membered S- and O-heterocycles

Zhao,

Liu,

Zhuang

et al. 2024

Chem. Sci.

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“…In recent times, our research group has been dedicated to the field of photoinduced palladium catalysis . Given the significance of benzoazepines in the realms of both biological and medicinal chemistry, we envisioned the possibility of synthesizing molecules of this class through a facile methodology.…”

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Accessing Benzoazepine Derivatives via Photoinduced Radical Relay Formal [5 + 2] Reaction of Amide/Alkyne Enabled by Palladium Catalysis

Du,

Sheng,

Tang

et al. 2024

Org. Lett.

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A novel class of alkyne-tethered amides facilitates an unprecedented photoinduced palladium-catalyzed radical relay formal [5 + 2] reaction. This innovative strategy allows for the rapid construction of diverse fused benzoazepine structures, yielding structurally novel and compelling compounds. With a broad substrate scope and excellent functional group tolerance, the methodology synthesizes biologically active compounds. Notably, the resulting tricyclic benzo[b]azepines offer diversification opportunities through simple transformations. DFT calculations elucidate a seven-membered ring closure mechanism involving the alkenyl radical and Pd(I) rebound alongside a concerted metalation−deprotonation (CMD) process.

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Direct electrochemical synthesis of arenesulfonyl fluorides from nitroarenes: a dramatic ionic liquid effect

Abstract: A practical electrochemical strategy for direct synthesis of arenesulfonyl fluorides from industrial feedstock nitroarenes is described. Key to success lies in using cheap ionic liquid N-methylimidazolium p-toluenesulfonate ([Mim]PhSO3) as an...

Cited by 14 publications

References 81 publications

Copper-Mediated Radical Fluorine-Atom Transfer to Sulfonyl Radical: A Dramatic 4-Methoxypyridine 1-Oxide Ligand Effect

Copper-Mediated Radical Fluorine-Atom Transfer to Sulfonyl Radical: A Dramatic 4-Methoxypyridine 1-Oxide Ligand Effect

CoH-catalyzed asymmetric remote hydroalkylation of heterocyclic alkenes: a rapid approach to chiral five-membered S- and O-heterocycles

Accessing Benzoazepine Derivatives via Photoinduced Radical Relay Formal [5 + 2] Reaction of Amide/Alkyne Enabled by Palladium Catalysis

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