Influence of Coordination to Silver(I) Centers on the Activity of Heterocyclic Iodonium Salts Serving as Halogen‐Bond‐Donating Catalysts DOI
Mikhail V. Il’in, Denis A. Polonnikov, Alexander S. Novikov

et al.

ChemPlusChem, Journal Year: 2023, Volume and Issue: 88(10)

Published: Sept. 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.

Language: Английский

2,2‐Difluoroethylation of Heteroatom Nucleophiles via a Hypervalent Iodine Strategy DOI Creative Commons
Suman Das,

Charlotte McIvor,

Andrew Greener

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 8, 2024

The 2,2-difluoroethyl group is an important lipophilic hydrogen bond donor in medicinal chemistry, but its incorporation into small molecules often challenging. Herein, we demonstrate electrophilic 2,2-difluoroethylation of thiol, amine and alcohol nucleophiles with a hypervalent iodine reagent, (2,2-difluoro-ethyl)(aryl)iodonium triflate, via proposed ligand coupling mechanism. This transformation offers complementary strategy to existing methods allows access wide range 2,2-difluoroethylated nucleophiles, including the drugs Captopril, Normorphine Mefloquine.

Language: Английский

Citations

5
Key-to-lock halogen bond-based tetragonal pyramidal association of iodonium cations with the lacune rims of beta-octamolybdate DOI Creative Commons
Natalia S. Soldatova, Amirbek D. Radzhabov, Daniil M. Ivanov

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(31), P. 12459 - 12472

Published: Jan. 1, 2024

The structure-directing "key-to-lock" interaction of double σ-(I

Language: Английский

Citations

5
Halonium, chalconium, and pnictonium salts as noncovalent organocatalysts: a computational study on relative catalytic activity DOI
Alexander S. Novikov, Dmitrii S. Bolotin

Organic & Biomolecular Chemistry, Journal Year: 2022, Volume and Issue: 20(38), P. 7632 - 7639

Published: Jan. 1, 2022

This theoretical study sheds light on the relative catalytic activity of pnictonium, chalconium, and halonium salts in reactions involving elimination chloride electrophilic activation a carbonyl group. DFT calculations indicate that for cationic aromatic onium salts, values electrostatic potential heteroatom σ-holes gradually increase from pnictogen- to halogen-containing species. The higher halogen atoms result overall these species, but case pnictonium chalconium cations, weak interactions side groups provide an additional stabilization effect reaction transition states. Based upon quantum-chemical calculations, phosphonium(V) arsenonium(V) is expected be too low obtain effective noncovalent organocatalytic compounds, whereas stibonium(V), telluronium(IV) iodonium(III) exhibit application as organocatalysts.

Language: Английский

Citations

22
Application of Thiourea/Halogen Bond Donor Cocatalysis in Metal-Free Cationic Polymerization of Isobutyl Vinyl Ether and Styrene Derivatives DOI
Koji Takagi,

Hiroto Murakata,

Tomoki Hasegawa

et al.

Macromolecules, Journal Year: 2022, Volume and Issue: 55(13), P. 5756 - 5765

Published: June 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.

Language: Английский

Citations

20
Influence of Coordination to Silver(I) Centers on the Activity of Heterocyclic Iodonium Salts Serving as Halogen‐Bond‐Donating Catalysts DOI
Mikhail V. Il’in, Denis A. Polonnikov, Alexander S. Novikov

et al.

ChemPlusChem, Journal Year: 2023, Volume and Issue: 88(10)

Published: Sept. 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.

Language: Английский

Citations

13