Electrochemical-Oxidation-Promoted Direct N-ortho-Selective Difluoromethylation of Heterocyclic <i>N</i>-Oxides

Zhang, Dong; Cai, Jinlin; Du, Jinze; Yang, Jinming; Geng, Rongqing; Fang, Zheng; Guo, Kai

doi:10.1021/acs.orglett.1c04241

Cited by 22 publications

(16 citation statements)

References 38 publications

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“…Similarly, the Zhang and Fang group recently reported the use of sodium difluoromethanesulfinate for the electrochemically induced difluoromethylation of quinoline and isoquinoline N-oxides. [134]…”

Section: Electrochemical Methodsmentioning

confidence: 99%

“…However, difluoromethylation and trifluoroethylation reactions were effective only for the most reactive substrates whereas trifluoromethylation was much more efficient in general, as it will be discussed later in this review article, which reflects the poorer reactivity of the CF 2 H • and CH 2 CF 3 • radical species with a range of heteroarenes (Scheme 51). Similarly, the Zhang and Fang group recently reported the use of sodium difluoromethanesulfinate for the electrochemically induced difluoromethylation of quinoline and isoquinoline N ‐oxides [134] …”

Section: Perfluoroalkylation Of (Hetero)arenesmentioning

confidence: 98%

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Direct Perfluoroalkylation of C−H Bonds in (Hetero)arenes

Baguia

Evano

2022

Chemistry A European J

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Perfluoroalkylated (hetero)arenes represent an extremely important family of molecules commonly utilized in many areas such as medicinal chemistry, agrochemistry and material sciences. Due to their unique properties, they have attracted significant interest from synthetic chemists and various methods have been developed for their synthesis. Among them, the direct perfluoroalkylation of C(sp 2 )À H bonds in (hetero)arenes is one of the most attractive and straightforward ones, provided that it proceeds with high levels of regioselectivity. In this review article, a comprehensive overview of advances in this field is presented, with a special focus on the reaction mechanisms involved in these transformations and their regioselectivity. All methods available have been classified according to the nature of the perfluoroalkyl chain introduced, trifluoromethylation reactions being overviewed in a separate section, and to the nature of the reagents/catalysts required.

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Section: Electrochemical Methodsmentioning

confidence: 99%

Section: Perfluoroalkylation Of (Hetero)arenesmentioning

confidence: 98%

Direct Perfluoroalkylation of C−H Bonds in (Hetero)arenes

Baguia

Evano

2022

Chemistry A European J

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“…Six-membered N -heteroarenes are important substructures found in numerous bioactive compounds. In most cases, functionality is incorporated into the pyridine ring system through pyridine ring synthesis or from commercial sources, which can limit access to more complex scaffolds. − C–H alkylation of heteroarenes, on the other hand, offers a direct method to prepare a diverse range of functionality from easily accessible starting materials. − Photocatalytic and electrochemical Minisci-like reactions that involve the addition of alkyl radicals to heteroarenes have allowed for the formation of new C–C bonds and the direct incorporation of diverse functionality. − The use, however, of external terminal oxidants, sacrificial electron donors, and expensive photocatalysts limits, to some extent, the overall utility.…”

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confidence: 99%

Desulfinative Alkylation of Heteroarenes via an Electrostatic Electron Donor–Acceptor Complex

2022

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Functionalized pyridine and quinoline rings are important components of numerous bioactive molecules and natural products; however, diversification of these rings often requires de novo heterocycle ring synthesis or demanding reaction conditions. We report a method for desulfinative alkylation of pyridine and quinoline N-methoxide salts that operates under both photocatalytic and electrostatic electron donor–acceptor-mediated pathways. Unlike most EDA-mediated processes, this reaction operates in the absence of light and with the desulfination of the donor compound.

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“…CV experiments showed that the C�C double bond in the product was formed via an addition−oxidation−elimination procedure. At the beginning, sulfonyl hydrazide (114) was activated at the anode by an iodide cation and yielded a radical species (117) at the anode; in this phase, the sulfonyl iodide (115) was proven to be a key intermediate. The radical (117) also could be gained from the sulfonyl iodide (115) via a sulfonyl anion intermediate (116).…”

Section: Sulfonylation Of Alkenes and Alkynesmentioning

confidence: 99%

The Application of Sulfonyl Hydrazides in Electrosynthesis: A Review of Recent Studies

2022

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Sulfonyl hydrazides are viewed as alternatives to sulfinic acids and their salts or sulfonyl halides, which are broadly used in organic synthesis or work as active pharmaceutical substances. Generally, sulfonyl hydrazides are considered good building blocks and show powerful value in a diverse range of reactions to construct C–S bonds or C–C bonds, and even C–N bonds as sulfur, carbon, or nitrogen sources, respectively. As a profound synthetic tool, the electrosynthesis method was recently used to achieve efficient and green applications of sulfonyl hydrazides. Interestingly, many unique and novel electrochemical syntheses using sulfonyl hydrazides as radical precursors have been developed, including cascade reactions, functionalization of heterocycles, as well as a continuous flow method combining with electrochemical synthesis since 2017. Accordingly, it is necessary to specifically summarize the recent developments of electrosynthesis with only sulfonyl hydrazides as radical precursors to more deeply understand and better design novel electrochemical synthesis reactions. Herein, electrosynthesis research using sulfonyl hydrazides as radical precursors since 2017 is reviewed in detail based on the chemical structures of products and reaction mechanisms.

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Electrochemical-Oxidation-Promoted Direct N-ortho-Selective Difluoromethylation of Heterocyclic N-Oxides

Cited by 22 publications

References 38 publications

Direct Perfluoroalkylation of C−H Bonds in (Hetero)arenes

Direct Perfluoroalkylation of C−H Bonds in (Hetero)arenes

Desulfinative Alkylation of Heteroarenes via an Electrostatic Electron Donor–Acceptor Complex

The Application of Sulfonyl Hydrazides in Electrosynthesis: A Review of Recent Studies

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