Synthesis of Stable Hypervalent Bromine(III) Complexes by in Situ Oxidation with Lewis Acids Containing sp-Hybridized Nitrogen DOI

Tomohiro Fujino,

Tadashi Hyodo, Yuko Otani

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(46), P. 10025 - 10029

Published: Nov. 11, 2024

Stable hypervalent bromine(III) compounds were synthesized via aryl bromine oxidation with

Language: Английский

Halogen, Chalcogen, Pnictogen, and Tetrel Bonding in Non‐Covalent Organocatalysis: An Update DOI Creative Commons
Dragana Jovanovic,

Meghana Poliyodath Mohanan,

Stefan M. Huber

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 11, 2024

The use of noncovalent interactions based on electrophilic halogen, chalcogen, pnictogen, or tetrel centers in organocatalysis has gained noticeable attention. Herein, we provide an overview the most important developments last years with a clear focus experimental studies and catalysts which act via such non-transient interactions.

Language: Английский

Citations

27

Easy access to polyhalogenated biaryls: regioselective (di)halogenation of hypervalent bromines and chlorines DOI Creative Commons
Daniel Carter Martos, Maxime De Abreu, Pascal Hauk

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(18), P. 6770 - 6776

Published: Jan. 1, 2024

Polyhalogenated biaryls are unique motifs offering untapped potential as versatile building blocks for the expedient synthesis of complex biaryl compounds.

Language: Английский

Citations

7

Cooperative Covalent–Noncovalent Organocatalysis of the Knoevenagel Condensation Based on an Amine and Iodonium Salt Mixture DOI
Alexandra A. Sysoeva, Mikhail V. Il’in, Dmitrii S. Bolotin

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(12)

Published: Feb. 21, 2024

Abstract The experimentally obtained kinetic data has indicated the existence of a synergetic cocatalytic effect provided by an iodonium salt in base‐catalyzed Knoevenagel condensation. diphenyliodonium triflate serving as halogen bond‐donating Lewis acid provides higher than zinc(II) or triflic serving, respectively, metal cation‐based and Brønsted acid. Such remains same for broad scope carbonyl compounds covering aldehydes featuring electron‐withdrawing electron‐donating substituents, well ketone involved reaction.

Language: Английский

Citations

4

Iodonium and Telluronium Triflates Serving as Noncovalent Organocatalysts Provide Catalytic Effect in the Schiff Condensation Due to Different Reasons DOI
Ivan O. Putnin, Alexandra A. Sysoeva, Mikhail V. Il’in

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: June 15, 2024

Abstract Sulfonium, selenonium, telluronium triflates, as well chloronium, bromonium, and iodonium triflates have been examined in the model Schiff condensation chalcogen‐ halogen bond donating organocatalysts, respectively. The kinetic data indicated that catalytic effect of salt is provided via decrease enthalpy activation reaction, whereas – unexpectedly caused by value entropy activation. In addition, it was experimentally shown activity sulfonium selenonium salts significantly lower than chloronium bromonium salts, but latter pair species less stable under reaction conditions former pair.

Language: Английский

Citations

4

Halonium and Chalconium Salt-Catalyzed Schiff Condensation: Kinetics and DFT Insights into Organocatalyst Activity Parameters DOI
Alexandra A. Sysoeva, Yana V. Safinskaya, Mikhail V. Il’in

et al.

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Chalconium and halonium salts catalyze Schiff condensation. Kinetic data DFT calculations show that the catalytic activity correlates with maximum electrostatic potential on σ-holes, whereas other factors are less significant.

Language: Английский

Citations

0

Extrapolation of PBBs Environmental Transformation Mechanisms and Toxicity Risks of Byproducts DOI Open Access
Bo-Han Xu, Qian Liu,

Weihan Cui

et al.

International Journal of Molecular Sciences, Journal Year: 2025, Volume and Issue: 26(4), P. 1753 - 1753

Published: Feb. 19, 2025

Polybrominated biphenyls (PBBs) are commonly used flame retardants that pose severe risks to humans. However, there is a lack of systematic research on the transformation process and biological toxicities PBBs in environment, which not conducive prevention control pollution PBBs. Therefore, pathways (i.e., photodegradation, microbial degradation, combustion oxidation, vivo metabolism) previously designed PBB substitutes were deduced first. Then potential rodent carcinogenicity, toxicity, mutagenicity, developmental skin eye irritation, sensitization, aquatic toxicity products evaluated using toxicokinetics (TOPKAT) model. Finally, 3D quantitative structure activity relationship (3D-QSAR) models constructed assess human hepatotoxicity, epigenetic neurotoxicity, immunotoxicity) PBBs, substitutes, their products. Results showed exhibit high toxicity) organisms. The D3-A1 molecule had highest carcinogenic risk probability at 0.826. dihydroxy metabolite 2,2'-OH-PBB-80 PBB-80 presented (toxicity 0.713). dibenzofuran (PBDF) strongest irritation (probability 0.995). oxidation exhibited higher ecological health than other Among humans, was theoretically significant, with characterization values ranging from 70.53 100.87. This first study comprehensively evaluate by combining inference prediction product toxicities, providing theoretical support for design environmentally friendly future studies.

Language: Английский

Citations

0

Electrochemical synthesis of cyclic biaryl λ3-bromanes from 2,2’-dibromobiphenyls DOI Creative Commons
Andrejs Savkins, Igors Sokolovs

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 451 - 457

Published: Feb. 27, 2025

The remarkable nucleofugality of bromoarenes in diarylbromonium species renders them particularly suitable for the generation arynes subsequent use a wide range synthetic applications. common approach to generate cyclic biaryl λ3-bromanes is based on thermal decomposition hazardous diazonium salts. Herein, we disclose mild and straightforward by direct anodic oxidation 2,2'-dibromo-1,1'-biphenyl. electrochemical method provides access symmetrically non-symmetrically substituted moderate yields.

Language: Английский

Citations

0

Diazomethyl-λ3-iodane meets aryne: Dipolar cycloaddition and C-to-N iodane shift leading to indazolyl-λ3-iodanes DOI Creative Commons

S. Otsuki,

Kazuya Kanemoto, Daniel Carter Martos

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Diazomethyl-λ 3 -iodanes have recently emerged as carbyne equivalents in organic synthesis, enabling the construction of multi-substituted carbon centers through strategic sequential activation diazo and iodane functional groups. Distinct from...

Language: Английский

Citations

0

Cyclic Diphenylchloronium-Salt-Triggered Coupling of Sulfides with Nucleophiles: Modular Assembly of Pharmaceuticals DOI

Bangxiong Kang,

Wei Li, Huanfeng Jiang

et al.

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

Published: April 2, 2025

We report a novel coupling strategy enabled by cyclic diphenylchloronium salt that facilitates reactions between sulfides and diverse nucleophiles, including oxygen- nitrogen-based species. The methodology efficiently produces structurally varied valuable compounds, carbamates, carboxylic esters, aryl ethers, alkylated amines, under mild, operationally simple conditions. protocol's synthetic utility was highlighted through modular preparation of five important drugs structural analogues, demonstrating significant potential for drug discovery applications.

Language: Английский

Citations

0

Nichtkovalente Organokatalyse mit Halogen‐, Chalkogen‐, Pniktogen‐ und Tetrelbrücken: neuere Entwicklungen DOI Creative Commons
Dragana Jovanovic,

Meghana Poliyodath Mohanan,

Stefan M. Huber

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(31)

Published: May 10, 2024

Abstract Die Anwendung nichtkovalenter Wechselwirkungen, welche auf elektrophilen Halogen‐, Chalkogen‐, Pniktogen‐ oder Tetrelzentren beruhen, hat in der Organokatalyse deutlich an Aufmerksamkeit gewonnen. Wir geben hier einen Überblick über die wichtigsten Entwicklungen letzten Jahre, mit einem Fokus experimentellen Studien und Katalysatoren, nicht‐transiente derartige Welchselwirkungen agieren.

Citations

2