Photoredox Fluoroalkylation of Hydrazones in Neutral and Reductive Modes

Worp, Boris A. van der; Kosobokov, Mikhail D.; Levin, Vitalij V.; Dilman, Alexander D.

doi:10.1002/adsc.202001381

Cited by 21 publications

(9 citation statements)

References 58 publications

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“…However, the presence of a second nitrogen decreases the electrophilic character of their C=N bond, resulting in decreased efficiency of addition of nucleophilic radicals. In contrast, reactions of hydrazones with fluorinated radicals are well developed, with particular emphasis on N,N ‐dialkyl‐substituted hydrazones [33–38] …”

Section: Methodsmentioning

confidence: 99%

Zinc Chelate Complexes of N‐Acyl Hydrazones as Substrates for Addition of Alkyl and Fluorinated Radicals

2023

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Zinc chelate complexes can be generated in situ from N‐acyl hydrazones by treatment with isopropyl zinc iodide. These complexes couple with alkyl and fluorinated radicals under photoredox conditions. Alkyl radicals were generated from organozinc halides using an organic photocatalyst and afford hydrazines as a result of reductive mode of addition. Fluorinated radicals were formed from perfluorinated alkyl iodides under photoredox conditions leading to fluoroalkylated hydrazones via neutral reaction pathway.

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Section: Methodsmentioning

confidence: 99%

Zinc Chelate Complexes of N‐Acyl Hydrazones as Substrates for Addition of Alkyl and Fluorinated Radicals

2023

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“…The primary products were not isolated, but were converted into 3-fluorofurans upon brief treatment of the reaction mixture with acid. [61] Compounds 9 containing tetrafluoropyridine fragment (PyfS) constitute another class of reagents, which were successfully employed in photoredox reactions based on cleavage of the CÀ S bond [63][64][65][66] (Scheme 12). They are obtained by thiol-ene addition to gem-difluorostyrenes catalyzed by 9phenylacrydine under irradiation.…”

Section: Silyl Enol Ethersmentioning

confidence: 99%

Visible‐Light Promoted Radical Fluoroalkylation of O‐ and N‐Substituted Alkenes

Levin

Dilman

2023

The Chemical Record

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Interaction of enol ethers enol acetates, enamides and enamines with fluorinated reagents may be considered as a reliable method for the synthesis of organofluorine compounds. While classic nucleophile/electrophile substitution or addition mechanisms cannot be realized for coupling of these components, their intrinsic reactivities are revealed with the aid of photoredox catalysis. A combination of these electron donating and accepting components provides a perfect balance needed for individual redox steps, which in some cases may proceed even without a photocatalyst. The same electronic factors also support the key C,C‐bond forming event involving addition of fluorinated radical at the electron rich double bond.

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“…[28][29][30][31] On the other hand, the desulfurization of the second class of thioethers (D or G) can be achieved by initial SET reduction of thioethers containing either tetra-fluoropyridine or thiazolium cores (Scheme 8B). [32][33][34][35][36][37][38][39][40] The splitting of the CÀ S bond in the radicals E or H then leads to the carbon radicals and either a stabilized thiolate F or the 3methylthiazolidine-2-thione J byproduct.…”

Section: Desulfurization Of Thioethersmentioning

confidence: 99%

Photo‐induced Desulfurative Processes for Carbon Radical Generation

et al. 2023

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Thiols constitute an important family among sulfur‐containing compounds, with well‐established applications in various fields ranging from medicine to material science. For instance, thiol residues are good hydrogen donors which reduce radical species in biological or chemical processes. However, even though the S‐H bond activation of thiols for providing access to thiyl radicals has been largely studied, desulfurative processes affording carbon‐based radicals by C‐S bond activation have been less explored. In recent years, photoredox catalysis has become the prevalent method for the generation of radicals under soft reaction conditions from readily available starting materials under visible light. In this context, recent studies have been devoted to the development of photocatalytic procedures aiming at the desulfurization of thiol derivatives leading to new C‐H, C‐C or C‐Het bond formation reactions. This review will cover the synthetic methodologies and strategies for photo‐mediated desulfurization of native thiols, thioethers, sulfonium salts and xanthates to access new organic compounds. This emerging field is especially interesting for new transformations of cysteine and peptide derivatives.

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Photoredox Fluoroalkylation of Hydrazones in Neutral and Reductive Modes

Cited by 21 publications

References 58 publications

Zinc Chelate Complexes of N‐Acyl Hydrazones as Substrates for Addition of Alkyl and Fluorinated Radicals

Zinc Chelate Complexes of N‐Acyl Hydrazones as Substrates for Addition of Alkyl and Fluorinated Radicals

Visible‐Light Promoted Radical Fluoroalkylation of O‐ and N‐Substituted Alkenes

Photo‐induced Desulfurative Processes for Carbon Radical Generation

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