The Ground State of Multispin Systems Based on Verdazyl and Nitrene Radicals: An EPR and Quantum-Chemical Study DOI

Alexandr S. Shmakov,

Matvey K. Shurikov, Денис В. Корчагин

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 31, 2024

In this study, low-temperature EPR spectroscopy and quantum-chemical techniques were employed to investigate multispin systems─1,5-diphenyl-3-(3-nitrenophenyl)-6-oxoverdazyl 1,5-diphenyl-3-(4-nitrenophenyl)-6-oxoverdazyl─that contain a nitrene center at either meta- or para-position, respectively. Ground states magnetic zero-field splitting (ZFS) parameters of these systems determined by experimental computational methods. The results indicated that the high-spin quartet state is ground state, quartet-doublet energy gap close 10 kcal/mol for para-position group, with ZFS D = 0.292 cm-1 E/D 0.002 cm-1. contrast, meta-position, low-spin doublet favored an 1 kcal/mol. observed difference in could be qualitatively explained analysis spin density distribution delocalization unpaired π-electron center. Overall, study provides valuable insights into electronic structures such systems.

Language: Английский

Transition-metal-free phosphorylation of polyfluoroarenes with P(O)H compounds DOI

Bingqian Sun,

Yongqiang Liang,

Meng-Ting Xiang

et al.

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: 23(10), P. 2358 - 2361

Published: Jan. 1, 2025

Herein, a base-promoted C-P(O) bond formation method has been developed for the phosphorylation of polyfluoroarenes through selective C-F cleavage. The high selectivity and mild, transition-metal-free conditions this underscore its potential sustainable synthesis applications. This expands scope polyfluoroarene functionalization, providing valuable tool incorporating phosphorus motifs in complex aromatic frameworks.

Language: Английский

Citations

0
Visible Light-Promoted Defluorinative Alkylation of Trifluoromethyl Ketones with α-Aminoalkyl Boron Species DOI
Yue Zhang, Kun Li, Zhihong Wang

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

In this study, we developed a photoredox-catalyzed defluorinative cross-coupling method for trifluoroketones and alkyl boronic acids. The reaction afforded series of novel α,α-difluoroketone derivatives, in vitro fungicidal activity revealed that some these compounds exhibited moderate to excellent against Rhizoctonia solani Botrytis cinerea. particular, compound 3d showed an EC50 value 4.27 μg/mL B. cinerea can be used as lead further optimization.

Language: Английский

Citations

0
Controlled synthesis of polymers in the light of green chemistry DOI
Д. Ф. Гришин, Ivan D. Grishin

Russian Chemical Reviews, Journal Year: 2025, Volume and Issue: 94(4), P. RCR5164 - RCR5164

Published: April 1, 2025

The discovery of reversible deactivation radical polymerization (RDRP), or controlled (CRP) has revolutionized the chemistry synthetic polymers. This strategy opened up way to polymer materials with architecture, composition, and functions. Currently, owing use novel approaches related chain deactivation, gone beyond synthesis. It can be used obtain not only macromolecular organic compounds, but also organic-inorganic hybrid materials, bioconjugates, promising polymers for electronics, energy production, medicine, other high-tech fields. is exceptionally important that some CRP methods have a clear-cut environmental component, since they are focused on compliance most principles green development nature-like processes in targeted synthesis well-defined specified set properties characteristics. review considers particular examples analyzes possible prospects practical application environmentally benign functional A comparative analysis performed classical living wide range monomers (reversible inhibition, addition fragmentation transfer, atom transfer involving transition metal complexes), concept photoredox catalysis, methodology as applied gives above aspects, including procedural details photoinitiation their relationship key principles. In our opinion, this will interest specialists field chemistry, chemists scientists. <br> bibliography includes 242 references.

Language: Английский

Citations

0
Polarity-Driven Thiyl Radical-Catalyzed Aerobic Debenzylation of Ethers and Amines DOI Creative Commons
Samuel W. Lardy,

Victoria Lerda,

Valerie A. Schmidt

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(20), P. 15062 - 15067

Published: Oct. 9, 2024

We report the use of a strongly electrophilic thiyl radical derived from commercially available pentafluorothiophenol as demonstration highly chemoselective H atom abstraction electron-rich and relatively weak benzylic C–H bonds adjacent to O N atoms. This approach enables selective oxidative removal benzyl p-methoxybenzyl groups amines ethers under ambient aerobic conditions.

Language: Английский

Citations

2
Current trends in organic chemistry: contribution of the N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences DOI
Mikhail P. Egorov, Valentine P. Ananikov, E. G. Baskir

et al.

Russian Chemical Bulletin, Journal Year: 2024, Volume and Issue: 73(9), P. 2423 - 2532

Published: Sept. 1, 2024

Language: Английский

Citations

2
Photocatalytic Functionalization of Alkenes Enabled by Polyfluoroaryl Migration DOI

Artem G. Savchenko,

Mikhail O. Zubkov, Jinbo Hu

et al.

ChemPhotoChem, Journal Year: 2024, Volume and Issue: 8(11)

Published: June 19, 2024

Abstract Visible light‐mediated photocatalytic approach for the radical functionalization of alkenes bearing fluorinated aryl sulfide fragment is described. The process occurs in presence organic photocatalyst using sulfinates as sources radicals. key step reaction intramolecular 1,4‐migration polyfluoroaryl group. In reaction, three new bonds are formed (two C−C and one C−S bond). decisive role fluorine atoms efficiency was confirmed by DFT calculations.

Language: Английский

Citations

1
Photoinduced, Redox-Neutral Decyanative and Defluorinative Phosphination of (Hetero)Arenes DOI

Conghui Wang,

Meizhong Tang,

Yating Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(38), P. 8154 - 8158

Published: Sept. 16, 2024

Triarylphosphines play a crucial role in organic synthesis as versatile components serving ligands, catalysts, and reactants. This study introduces metal-free, visible-light-induced method for the cross-coupling of cyanopyridines or polyfluoroarenes with diarylphosphines. approach facilitates formation C(sp

Language: Английский

Citations

1
Polyfluorinated benzoic acids as promising reagents for organic synthesis and medicinal chemistry DOI
Evgeny V. Shchegolkov, Yanina V. Burgart,

Irina V. Shchur

et al.

Russian Chemical Reviews, Journal Year: 2024, Volume and Issue: 93(8), P. RCR5131 - RCR5131

Published: Aug. 1, 2024

Polyfluoroaromatic compounds occupy a special place in organic synthesis due to wide range of their chemical transformations and unique biological properties. The introduction the carboxyl function into polyfluoroarenes allows further diversification chemistry these compounds. This review summarizes data on polyfluorobenzoic acids, including derivatives polyfluorosalicylic acids. reactions esterification, amidation, reduction, decarboxylation, metal-catalyzed decarboxylative cross-coupling, C–H functionalization, reductive defluorination, nucleophilic aromatic substitution, heterocyclization complex formation are considered. Reactivity features polyfluorobenzoates comparison non-fluorinated counterparts highlighted. potential for practical applications acid derivatives, primarily as biologically active compounds, is presented. <br> Bibliography includes 300 references.

Language: Английский

Citations

0
The Ground State of Multispin Systems Based on Verdazyl and Nitrene Radicals: An EPR and Quantum-Chemical Study DOI

Alexandr S. Shmakov,

Matvey K. Shurikov, Денис В. Корчагин

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 31, 2024

In this study, low-temperature EPR spectroscopy and quantum-chemical techniques were employed to investigate multispin systems─1,5-diphenyl-3-(3-nitrenophenyl)-6-oxoverdazyl 1,5-diphenyl-3-(4-nitrenophenyl)-6-oxoverdazyl─that contain a nitrene center at either meta- or para-position, respectively. Ground states magnetic zero-field splitting (ZFS) parameters of these systems determined by experimental computational methods. The results indicated that the high-spin quartet state is ground state, quartet-doublet energy gap close 10 kcal/mol for para-position group, with ZFS D = 0.292 cm-1 E/D 0.002 cm-1. contrast, meta-position, low-spin doublet favored an 1 kcal/mol. observed difference in could be qualitatively explained analysis spin density distribution delocalization unpaired π-electron center. Overall, study provides valuable insights into electronic structures such systems.

Language: Английский

Citations

0