Fluorination of fluoro-cyclobutene with high-valency metal fluoride

Mizukado, Junji; Matsukawa, Yasuhisa; Quan, Hengdao; Tamura, Masanori; Sekiya, Akira

doi:10.1016/j.jfluchem.2005.10.007

Cited by 10 publications

(3 citation statements)

References 17 publications

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“…Fluorination proceeded with 7 % yield determinated by NMR and GC‐MS. Similar yield has been observed using CoF 3 as fluorinating agent under the same conditions [177] …”

Section: Silver In C−h Bond Functionalizationsupporting

confidence: 83%

Application of Silver Compounds in Fluoroorganic Synthesis: A Minireview

2023

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The mini‐review is focused on application of silver and its compounds in fluoroorganic synthesis, and it reflects immense progress in this field which took place during the last two decades, with additional examples of reactivity of historical importance. Reactions of C−H, C−F, N−H and O−H bond functionalization, as well as catalysis of cycloaddition reactions and intramolecular rearrangement, retro‐rearrangement, and functional group migrations, have been described. Whenever available in original works, the reaction mechanisms were discussed. Since silver may be catalytically active in each of its available oxidation states from (0), via (I) and (II) to (III) with their immensely diverse properties, the organofluorine part is preceded by a brief overview of chemistry of silver in general. Uniqueness of silver among Group 11 elements is highlighted.

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“…Fluorination proceeded with 7 % yield determinated by NMR and GC‐MS. Similar yield has been observed using CoF 3 as fluorinating agent under the same conditions [177] …”

Section: Silver In C−h Bond Functionalizationsupporting

confidence: 83%

Application of Silver Compounds in Fluoroorganic Synthesis: A Minireview

2023

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“…It would be of considerable interest to have confirmation of the predictions of Table . Most of the cyclobutanes therein have been synthesized, − but to our knowledge thermodynamic determinations and uses of the data therefrom have been limited to RSE estimation only for c -C 4 F 8 . Extending this to other highly substituted cyclobutanes will require obtaining currently unavailable enthalpies of formation, such as that for c -C 4 Me 8 .…”

Section: Discussionmentioning

confidence: 99%

Application of a Semi-homodesmotic Approach in Estimating Ring Strain Energies (RSEs) of Highly Substituted Cyclobutanes: RSEs forc-C₄R₈That Make Sense

Gilbert

2014

J. Phys. Chem. A

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A semi-homodesmotic method for estimating of ring strain energies (RSEs) of substituted cyclopropanes is applied to substituted cyclobutanes c-C4HxR8-x (R = F, Cl, Me; x = 0, 2, 4). Whereas (hyper)homodesmotic reaction methods predict implausible results, particularly for c-C4R8, the semi-homodesmotic approach provides RSEs consistent with thermodynamic and independent computational data regardless of the degree of substitution. The method requires employing homodesmotic group equivalent reactions only for disubstituted cyclobutanes, relying solely on absolute energy calculations for more substituted rings. We find that, consistent with QTAIM data, RSEs increase with substitution regardless of the electronic nature of R, although the increase is more dramatic when R is electron-withdrawing. Overall, the semi-homodesmotic method is simpler than hyperhomodesmotic approaches and gives more trustworthy results.

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“…The difluoromethyl ether moiety has been found in several potential drug candidates due to the unique chemical and physical properties that enhance bioefficacy. − While synthetic strategies for difluoromethyl aryl ether synthesis have been developed, ,− very few have been applied to chiral secondary alcohols. Synthetic methods to prepare difluoromethyl ethers can be divided into four main groups: (a) C–O coupling reaction using a OCF 2 H synthon, , (b) transformation of esters and thioesters into difluoroethers, − (c) nucleophilic substitution pathways such as halogen displacement or nucleophilic attack of the alcohol to an electrophilic difluoromethyl source, ,− and (d) difluoromethylation of aryl and alkyl alcohols using a variety of difluorocarbene sources ,− (Figure ).…”

Section: Introductionmentioning

confidence: 99%

Rapid Multikilogram Scale-Up of Di- and Trifluoromethoxy Proline Derivatives

Cabrera,

Allais,

Arcari

et al. 2024

Org. Process Res. Dev.

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This report describes the synthesis, development, and scale-up (up to 10 kg) of di-and trifluoromethoxy prolines, key fragments evaluated in the development of potential antiviral SARS-CoV2 M pro inhibitors. We first demonstrate a scalable route to 1tert-butyl 2-methyl (2S,4R)-4-(difluoromethoxy)pyrrolidine-1,2-dicarboxylate employing a Cu-catalyzed difluoromethylation of alcohols using 2,2-difluoro-2-(fluorosulfonyl)acetic acid. We then demonstrate the optimization and scale-up of challenging 1-tertbutyl 2-methyl (2S,4R)-4-(trifluoromethoxy)pyrrolidine-1,2-dicarboxylate through silver-mediated oxidative trifluoromethylation of the corresponding alcohol. Finally, we report on the oxidative fluoro-desulfurization of xanthates as a potentially scalable route to access chiral aliphatic trifluoromethoxy ethers.

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Fluorination of fluoro-cyclobutene with high-valency metal fluoride

Cited by 10 publications

References 17 publications

Application of Silver Compounds in Fluoroorganic Synthesis: A Minireview

Application of Silver Compounds in Fluoroorganic Synthesis: A Minireview

Application of a Semi-homodesmotic Approach in Estimating Ring Strain Energies (RSEs) of Highly Substituted Cyclobutanes: RSEs forc-C₄R₈That Make Sense

Rapid Multikilogram Scale-Up of Di- and Trifluoromethoxy Proline Derivatives

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Fluorination of fluoro-cyclobutene with high-valency metal fluoride

Cited by 10 publications

References 17 publications

Application of Silver Compounds in Fluoroorganic Synthesis: A Minireview

Application of Silver Compounds in Fluoroorganic Synthesis: A Minireview

Application of a Semi-homodesmotic Approach in Estimating Ring Strain Energies (RSEs) of Highly Substituted Cyclobutanes: RSEs forc-C4R8That Make Sense

Rapid Multikilogram Scale-Up of Di- and Trifluoromethoxy Proline Derivatives

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Application of a Semi-homodesmotic Approach in Estimating Ring Strain Energies (RSEs) of Highly Substituted Cyclobutanes: RSEs forc-C₄R₈That Make Sense