Organocatalytic Friedel–Crafts arylation of aldehydes with indoles utilizing N-heterocyclic iod(az)olium salts as halogen-bonding catalysts

Green Chemistry, Год журнала: 2023, Номер 26(2), С. 825 - 831

Опубликована: Ноя. 15, 2023

Halogen-bonding catalysis enables the organocatalytic Fridel–Crafts arylation of aldehydes with indoles.

Язык: Английский

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Hypervalent Iodine (III)‐Based Complexation for Chiroptical Supramolecular Glass, Deep Eutectic Solvent and Luminescent Switch

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Июль 16, 2024

Hypervalent iodine(III) have widely been utilized for organic synthetic reagents. They are also recognized as positive charge-assisted, exceptionally robust biaxial halogen bond donors, while their potential in supramolecular materials is barely explored. This work reports a cyclic diaryliodonium ion bonding donor that displays remarkable binding affinity toward phenanthroline or acridine acceptors with chiral pendants. Biaxial enables chiroptical evolution solution, allowing rational control over chirality. Leveraging strong affinity, the complexes manifested amorphous properties and deep eutectic behavior solid state. Capitalizing on these attributes, this achieves successful preparation of glasses solvents. Additionally, appended light irradiation-triggered luminescence through hydrogen atom transfer process, showing applications anti-counterfeit display.

Язык: Английский

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Application of Thiourea/Halogen Bond Donor Cocatalysis in Metal-Free Cationic Polymerization of Isobutyl Vinyl Ether and Styrene Derivatives

Macromolecules, Год журнала: 2022, Номер 55(13), С. 5756 - 5765

Опубликована: Июнь 27, 2022

Cationic polymerization of isobutyl vinyl ether (IBVE) was investigated using Schreiner's thiourea (STU) combined with Im-TEPB bearing a 2-iodoimidazolium cation and noncoordinating borate anion. Both the CF3CO2H adduct HCl IBVE had ability to initiate polymerization, but number-averaged molecular weight rather low compared theoretical value distribution fairly broad (Mw/Mn > 2.6). On other hand, fast cationic p-methoxystyrene (pMOS, 50 equiv relative pMOS·HCl) proceeded STU/Im-TEPB cocatalysts, giving rise poly(pMOS) Mn = 4580 Mw/Mn 1.38. STU/Im-TfO exhibited decreased activity due coordination trifluoromethanesulfonate counteranion NH group STU, which supported by NMR spectrum, DFT calculation, UV–vis titration experiment. The could be roughly regulated cocatalysis between 2400 7500 monomer feed ratio keeping below 1.41, although these values were lower than ones probably unignorable chain-transfer reaction. kinetics revealed that consumption rate depends on concentration reveals catalytic function STU/Im-TEPB.

Язык: Английский

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Influence of Coordination to Silver(I) Centers on the Activity of Heterocyclic Iodonium Salts Serving as Halogen‐Bond‐Donating Catalysts

ChemPlusChem, Год журнала: 2023, Номер 88(10)

Опубликована: Сен. 7, 2023

Kinetic data based on 1 H NMR monitoring and computational studies indicate that in solution, pyrazole-containing iodonium triflates silver(I) triflate bind to each other, such an interplay results the decrease of total catalytic activity mixture these Lewis acids compared separate catalysis Schiff condensation, imine-isocyanide coupling, or nucleophilic attack a triple carbon-carbon bond. Moreover, kinetic cooperation with prevention decomposition salts during reaction progress. XRD study confirms coordinates center via pyrazole N atom produce rare example pentacoordinated trigonal bipyramidal dinuclear complex featuring cationic ligands.

Язык: Английский

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Chalcogen- and Halogen-Bond-Donating Cyanoborohydrides Provide Imine Hydrogenation

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(5), С. 2916 - 2925

Опубликована: Фев. 19, 2024

Sulfonium, selenonium, telluronium, and iodonium cyanoborohydrides have been synthesized, isolated, fully characterized by various methods, including single-crystal X-ray diffraction (XRD) analysis. The quantum theory of atoms in molecules' analysis based on the XRD data indicated that hydride···σ-hole short contacts observed crystal structures each compound a purely noncovalent nature. telluronium provide significantly higher rate model reaction imine hydrogenation compared with sodium tetrabutylammonium cyanoborohydrides. Based NMR high-resolution electrospray ionization mass spectrometry indicating progress is accompanied cation reduction, mechanism involving intermediate formation elusive onium hydrides has proposed as an alternative to conventional electrophilic activation moiety its ligation cation's σ-hole.

Язык: Английский

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