Photoredox-catalyzed deoxyfluorination of activated alcohols with Selectfluor®

González‐Esguevillas, María; Miró, Javier; Jeffrey, Jenna L.; MacMillan, David W. C.

doi:10.1016/j.tet.2019.05.043

Cited by 61 publications

(51 citation statements)

References 37 publications

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“…19. c Yields determined by 19 F-NMR using 1-fluoronaphthalene as an external standard. d General conditions except 0.4 M, 1.5 equiv.…”

Section: Resultsmentioning

confidence: 99%

Nucleophilic (Radio)Fluorination of Redox-Active Esters via Radical-Polar Crossover Enabled by Photoredox Catalysis

Webb¹,

Park²,

Cole³

et al. 2020

Preprint

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<p>We report a redox-neutral method for nucleophilic fluorination of N-hydroxyphthalimide esters using an Ir photocatalyst under visible light irradiation. The method provides access to a broad range of aliphatic fluorides, including primary, secondary, and tertiary benzylic fluorides as well as unactivated tertiary fluorides, that are typically inaccessible by nucleophilic fluorination due to competing elimination. In addition, we show that the decarboxylative fluorination conditions are readily adapted to radiofluorination with [<sup>18</sup>F]KF. We propose that the reactions proceed by two electron transfers between the Ir catalyst and redox-active ester substrate to afford a carbocation intermediate that undergoes subsequent trapping by fluoride. Examples of trapping with O- and C-centered nucleophiles and deoxyfluorination via N-hydroxyphthalimidoyl oxalates are also presented, suggesting that this approach may offer a general blueprint for affecting redox-neutral SN1 substitutions under mild conditions.</p>

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“…19. c Yields determined by 19 F-NMR using 1-fluoronaphthalene as an external standard. d General conditions except 0.4 M, 1.5 equiv.…”

Section: Resultsmentioning

confidence: 99%

Nucleophilic (Radio)Fluorination of Redox-Active Esters via Radical-Polar Crossover Enabled by Photoredox Catalysis

Webb¹,

Park²,

Cole³

et al. 2020

Preprint

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“…[45] Owing to the flexible conformational behavior of fluorinated cyclopentanes, there has been some interest in the preparation of their mono-and recently multi-fluorinated ana-logues, such as the all-cis-1,2,3,4-tetrafluorocyclopentane 15 (Figure 5). [46,47] The X-ray analysis of the latter indicates an envelope conformation with an axial fluorine at the tip. According to computations however, the latter conformation might be different in gas phase or in solution.…”

Section: Fluorine Orientation In Five-membered Ringsmentioning

confidence: 99%

Fluorinated Rings: Conformation and Application

Mondal

Agbaria

Nairoukh

2021

Chemistry A European J

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The introduction of fluorine atoms into molecules and materials across many fields of academic and industrial research is now commonplace, owing to their unique properties. A particularly interesting feature is the impact of fluorine substitution on the relative orientation of a C−F bond when incorporated into organic molecules. In this Review, we will be discussing the conformational behavior of fluorinated aliphatic carbo‐ and heterocyclic systems. The conformational preference of each system is associated with various interactions introduced by fluorine substitution such as charge‐dipole, dipole‐dipole, and hyperconjugative interactions. The contribution of each interaction on the stabilization of the fluorinated alicyclic system, which manifests itself in low conformations, will be discussed in detail. The novelty of this feature will be demonstrated by presenting the most recent applications.

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“…19) In this context, functionalizing the C2′ positions of acetogenins is an attractive research topic; however, to the best of our knowledge, only a single report has been published into C2′-chlorinated analogs, which were synthesized by the Appel reactions of natural C2′-hydroxy acetogenins. 25) Recently, some efficient late-stage deoxy-fluorinations of secondary alcohols have also been reported 26,27) ; however, it may be difficult to apply this method to the syntheses of C2′-fluorinated acetogenins, since natural acetogenins contain highly reactive chiral α,β-unsaturated-γ-lactone moieties that are easily epimerized. 28) With this in mind, we herein report the details of the syntheses of C2′-fluorinated solamin 1 and its C2′-diastereomer.…”

Section: Introductionmentioning

confidence: 99%

Syntheses of C2′-Fluorinated Analogs of Solamin

et al. 2020

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The details of the total syntheses of C2′-fluorinated analogs of solamin, an antitumor annonaceous acetogenin, are described. Fluorine was enantioselectively introduced at the C2′-position by organocatalytic α-fluorination of the aldehyde according to a previously reported method. C2′-fluorinated solamin and its C2′-diastereomer were synthesized by the Sonogashira coupling of a tetrahydrofuran fragment and fluorinecontaining γ-lactone fragments.

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Photoredox-catalyzed deoxyfluorination of activated alcohols with Selectfluor®

Cited by 61 publications

References 37 publications

Nucleophilic (Radio)Fluorination of Redox-Active Esters via Radical-Polar Crossover Enabled by Photoredox Catalysis

Nucleophilic (Radio)Fluorination of Redox-Active Esters via Radical-Polar Crossover Enabled by Photoredox Catalysis

Fluorinated Rings: Conformation and Application

Syntheses of C2′-Fluorinated Analogs of Solamin

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