Synthesis of superacidic carbon acid and its derivatives

Yanai, Hikaru; Taguchi, Takeo

doi:10.1016/j.jfluchem.2014.11.006

Cited by 27 publications

(10 citation statements)

References 70 publications

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“…Even in water, 3 a-Na showed a PLE band maximum of 533 nm with 0.80 of F PLE (entries 6 and 7). Similar substituent effects by the carbanionic substituent towards water solubility and log D were observed not only in the series of BODIPYs but also in fluorescein and aminocoumarin dyes (entries [8][9][10][11]. That is, 5-Na and 7-Na showed significant enhancement of lipophilicity as well as water solubility.…”

Section: Angewandte Chemiesupporting

confidence: 61%

“…However, recent progress on highly stable and isolable carbanion-containing salts motivated us. [7,8] Among them, inter-or intramolecular salts bearing Tf 2 C À group(s), which is a chemically inert carbanionic substituent, were reported one after another. [9] Utilization of this carbanionic group is attractive in the context of controlling macroscopic properties because of its ionic character and trivalency of the carbon center permitting to place a couple of triflyl groups and a linker to the functional moiety on it.…”

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confidence: 99%

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A Fluorinated Carbanionic Substituent for Improving Water Solubility and Lipophilicity of Fluorescent Dyes

et al. 2021

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Installation of a carbanionic substituent, that is strongly stabilized by two (trifluoromethyl)sulfonyl (Tf = SO 2 CF 3) groups, into several fluorescence dyes including boron-dipyrromethenes (BODIPYs), fluoresceins, and aminocoumarins has been achieved by the 2,2-bis(triflyl)ethylation reaction of the dye frameworks with highly electrophilic Tf 2 C = CH 2 , followed by neutralization with NaHCO 3. Despite the contradiction between water solubility and lipophilicity, the carbanion-decorated dyes thus obtained showed significant enhancement of not only water solubility but also lipophilicity. This work clearly demonstrates that the fluorinated, highly stabilized carbanionic substituent is a new option for controlling the macroscopic property of chemical materials. Water solubility (and aqueous solubility) is a key macroscopic property for chemical materials directed towards biorelevant applications. [1] The most common way to improve the water solubility of less soluble compounds is introduction of ionic groups such as the sulfonato group into the molecular structure (Figure 1 A). However, such ionic functionalities

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Section: Angewandte Chemiesupporting

confidence: 61%

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confidence: 99%

A Fluorinated Carbanionic Substituent for Improving Water Solubility and Lipophilicity of Fluorescent Dyes

et al. 2021

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“…To our delight, it was found that 0.2 equiv. of triflic acid (TfOH), one member of superacid family, [15,16] enabled the transformation to afford the desired disaccharide 5 a in 48 % yield at room temperature (rt) in 1 h (entry 3). Switching from 4 Å MS to 5 Å MS, the outcome of the coupling was further improved, and 5 a was obtained in 86 % yield (entry 4).…”

Section: Resultsmentioning

confidence: 99%

Triflic Imide‐Catalyzed Glycosylation of Disarmed Glycosyl ortho‐Isopropenylphenylacetates and ortho‐Isopropenylbenzyl Thioglycosides

Qiao

Wang

et al. 2022

Eur J Org Chem

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Glycosylation reaction involving the coupling of a glycosyl donor with a glycosyl acceptor is one of the cornerstones of chemical preparation of pure glycans and glycoconjugates of biological relevance. Catalytic glycosylation of glycosyl ester donors and thioglycosides is an attractive but underexplored topic in carbohydrate chemistry. Herein, triflic imide (Tf 2 NH)catalyzed glycosylation of various O-, S-, and C-nucleophiles has been achieved using disarmed glycosyl ortho-isopropenylphenylacetates (GIPPAs) and ortho-isopropenylbenzyl thioglycosides as glycosylating agents. The reactions proceed under mild conditions to give the desired glycosides in good-to-excellent yields. Of particular note, the comparable reactivity for the αisomers and the β-ones of GIPPAs is observed. The mechanistic investigation demonstrates that the isopropenyl group is essential for the reaction and its preferential protonation triggers the reaction. This work provides another member to the arsenals of glycosyl ester and thioglycoside donors suitable for acid-catalyzed glycosylation to create various glycosidic bonds.

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“…On the contrary, NMR data of 4 demonstrate the preference of a nearly planar s‐ cis ,s‐ cis conformer. Comparison of 13 C NMR data of gem ‐bis(triflyl)diene 5 and isolable zwitterions 6 and 7 reveals more details about the electronic state (Figure ). Because δ C2 in 3 is close to the values of the anionic carbon atoms in 6 and 7 (65.5 and 68.9 ppm, respectively), the charge‐separated resonance structure D can be considered the main contributor.…”

Section: Figurementioning

confidence: 99%

Chemical Bonding in Polarised Push–Pull Ethylenes

et al. 2019

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1,1‐Diamino‐2,2‐bis(triflyl)ethylenes with both twisted and planar structures around the partial “C=C” bond were synthesised. Bonding properties in these compounds were analysed by an experimental approach using high‐resolution X‐ray diffraction data treated with X‐ray wavefunction refinement (XWR). In the twisted compound, a dominant contribution of the charge‐separated resonance structure was revealed. On the contrary, the nearly planar compound still showed π‐bonding character, however, with a considerable contribution of the charge‐separated resonance structure.

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Synthesis of superacidic carbon acid and its derivatives

Cited by 27 publications

References 70 publications

A Fluorinated Carbanionic Substituent for Improving Water Solubility and Lipophilicity of Fluorescent Dyes

A Fluorinated Carbanionic Substituent for Improving Water Solubility and Lipophilicity of Fluorescent Dyes

Triflic Imide‐Catalyzed Glycosylation of Disarmed Glycosyl ortho‐Isopropenylphenylacetates and ortho‐Isopropenylbenzyl Thioglycosides

Chemical Bonding in Polarised Push–Pull Ethylenes

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