Tris(trimethylsilyl)silane in Photochemical Hydrodesulfurization─Methodology and Pyrophoricity DOI

Michaela Čierna,

Blažej Horváth,

Filip Pančík

и другие.

Organic Process Research & Development, Год журнала: 2024, Номер 28(11), С. 4156 - 4162

Опубликована: Окт. 30, 2024

A novel visible-light-induced hydrodesulfurization of a thioacetal was developed. The reaction operates under mild conditions using user-friendly tris(trimethylsilyl)silane as the reductant and low catalyst loading photoactive 4CzIPN. expansion scope thwarted by operationally hazardous nature process, occasionally producing fire. Careful examination mixtures allowed to identify silane (SiH4) likely culprit causing pyrophoricity.

Язык: Английский

Transition Metal and Photocatalyst Free Arylation via Photoexcitable Electron Donor Acceptor Complexes:Mediation and Catalysis DOI
Alexey A. Volkov, Dmitry I. Bugaenko, Alexander V. Karchava

и другие.

ChemCatChem, Год журнала: 2024, Номер 16(11)

Опубликована: Янв. 15, 2024

Abstract Visible‐light‐activated organic reactions unlock novel avenues for complex molecular transformations, impossible under standard “thermal” conditions, which makes them powerful tools in the arsenal of synthetic chemistry. However, transition metal‐based or photoredox catalysts are often used to ensure productive absorption visible light, might be not desirable medicinal chemistry and industry due toxicity, low sustainability, high cost most photocatalysts. A more environmentally economically benign approach is based on formation transient electron donor‐acceptor (EDA) complexes between two reagents a reagent an additive, that readily absorb acting as internal photosensitizers. Within EDA complex‐based arylation strategies, chemical transformations mediated by noncovalent interaction molecules, namely electron‐poor aryl halides their equivalents electron‐rich nucleophilic additives. Moreover, besides stoichiometric organocatalysis can achieved certain cases through regeneration donor molecules course reaction. Photoexcitation induces single transfer (SET) process generate radical species step. This Review will focus state‐of‐the‐art strategies utilizing halides, aryldiazonium, diaryliodonium, arylsulfonium arylphosphonium salts reactants, published mainly last five years.

Язык: Английский

Процитировано

8

Photoinduced Radical Desulfurative C(sp3)–C(sp2) Coupling via Electron Donor–Acceptor Complexes DOI
Jiaxuan Shen, Jincan Li, Meijun Chen

и другие.

Organic Letters, Год журнала: 2024, Номер 26(7), С. 1495 - 1500

Опубликована: Фев. 9, 2024

Herein, we disclose a radical desulfurative C–C coupling protocol for the synthesis of 4-alkylpyridines. A variety substituents on both benzyl thiols and 4-cyanopyridines are tolerated. The reaction is carried out under mild photocatalyst- transition-metal-free conditions. Preliminary mechanistic studies show that an electron donor–acceptor complex formed between alkaline Then, 1°, 2°, 3° C(sp3)-centered radicals was by cleavage C–S bond, 4-alkylpyridines were achieved through radical–radical with pyridyl anion.

Язык: Английский

Процитировано

8

Peptide macrocyclisation via intramolecular interception of visible-light-mediated desulfurisation DOI Creative Commons

Frances R. Smith,

Declan Meehan,

Rhys C. Griffiths

и другие.

Chemical Science, Год журнала: 2024, Номер 15(25), С. 9612 - 9619

Опубликована: Янв. 1, 2024

Herein, we report a peptide cyclisation strategy via intramolecular interception of cysteine desulfurisation. This method enables the unprotected peptides in aqueous solution installation hydrocarbon linkage.

Язык: Английский

Процитировано

3

Visible‐light Organic Photosensitizers Based on 2‐(2‐Aminophenyl)benzothiazoles for Photocycloaddition Reactions DOI Creative Commons
Ekaterina K. Pylova, Benjamin Lasorne, Nathan D. McClenaghan

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер 30(68)

Опубликована: Июль 16, 2024

We have studied 2-(2-aminophenyl)benzothiazole and related derivatives for their photophysical properties in view of employing them as new readily tunable organic photocatalysts. Their triplet energies were estimated by DFT calculations to be the range 52-57 kcal mol-1, suggesting suitability [2+2] photocycloaddition unsaturated acyl imidazoles with styrene derivatives. Experimental studies shown that 2-(2-aminophenyl)benzothiazoles comprising alkylamino groups (NHMe, NHiPr) or native amino group provide best photocatalytic results these visible-light mediated reactions without need any additives, yielding a cyclobutane A combined experimental theoretical approach has provided insights into underlying triplet-triplet energy transfer process.

Язык: Английский

Процитировано

3

Electrochemical Preparation and Transformation of Sulfonium Salts DOI Creative Commons
Takuya Michiyuki, Lutz Ackermann

ChemElectroChem, Год журнала: 2025, Номер unknown

Опубликована: Март 5, 2025

Abstract Sulfonium salts are typically bench‐stable and readily available reagents that showcase diverse chemical reactivities. Owing to these synthetically valuable features, sulfonium salt chemistry has witnessed considerable momentum over the past decades. Particularly, merger of electrosynthesis enabled utilization electric current in place cost‐intensive hazardous redox agents maximize attractive characteristics salts. Additionally, electrochemistry allowed chemists dial desired potential, offering selective access target products otherwise unattainable by either thermal or photochemical manifolds. These advantages led major advances chemistry. Thus, we, herein, provide an overview early pioneering findings recent progress devoted organic associated with until December 2024, aiming stimulate future this rapidly evolving arena.

Язык: Английский

Процитировано

0

Visible-Light-Driven Desulfurization Reaction Using Partially Oxidized TiN Nanoparticles as Photocatalysts DOI

Matas Simukaitis,

Shea Stewart, Yugang Sun

и другие.

The Journal of Physical Chemistry C, Год журнала: 2025, Номер unknown

Опубликована: Март 30, 2025

Desulfurization represents an important process in chemical synthesis that produces new molecules and accesses useful carbon radicals. Photocatalytically driving the reactions under broadband visible light illumination is still challenging due to high cost of noble metal complex photocatalysts controlled inert atmospheres widely used reported methods. This work uses partially oxidized TiN nanoparticles comprising earth-abundant elements as drive desulfurization methyl thioglycolate ambient atmosphere with a LED lamp. The yield product, acetate, up 73% after reaction for 18 h. generation accessible radicals confirmed by forming C–C coupling products styrene. results shed on promise modified nanoparticles, which possess strong optical absorption originating from localized surface plasmon resonances (LSPRs), facilitate using light.

Язык: Английский

Процитировано

0

Thioglycoside functionalization via chemoselective phosphine acceleration of a photocatalytic thiol-ene reaction DOI Creative Commons

Arun Kumar Thangarasu,

Charlie Fehl

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Green, operationally simple, and chemoselective access to thioglycoside analogs using mild photoredox condition in water.

Язык: Английский

Процитировано

0

Red Light and Supersilane: A Novel Pathway for Hydrofunctionalizations and Giese Reactions DOI Creative Commons
Aakanksha Gurawa, Marc Taillefer, Alexis Prieto

и другие.

ACS Organic & Inorganic Au, Год журнала: 2025, Номер unknown

Опубликована: Май 10, 2025

Язык: Английский

Процитировано

0

Protein desulfurization and deselenization DOI
Vincent Diemer, Eliott Roy, Vangelis Agouridas

и другие.

Chemical Society Reviews, Год журнала: 2024, Номер 53(17), С. 8521 - 8545

Опубликована: Янв. 1, 2024

Methods enabling the dechalcogenation of thiols or selenols have been investigated and developed for a long time in fields research as diverse study prebiotic chemistry, engineering fuel processing techniques, biomolecule structures function chemical synthesis biomolecules. The thiol selenol amino acids is nowadays particularly flourishing area being pillar modern protein synthesis, when used combination with selenol-based chemoselective peptide ligation chemistries. This review offers comprehensive scholarly overview field, emphasizing emerging trends providing detailed critical mechanistic discussion methods so far. Taking advantage recently published reports, it also clarifies some unexpected desulfurization reactions that were observed past which no explanation was provided at time. Additionally, includes on principal within framework newly introduced green chemistry metrics toolkits, well-rounded exploration subject.

Язык: Английский

Процитировано

2

Photoinduced Radical Approach for Desulfurative Alkylation of Cysteine Derivatives to Make Unnatural Amino Acids DOI
Pei Xu, Yiqin Liu,

Hui-Xian Jiang

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Окт. 4, 2024

Unnatural amino acids (UAAs) are highly valuable molecules in organic synthesis, pharmaceutical sciences, and material science. Herein, we present a photocatalytic radical approach for desulfurative alkylation of cysteine derivatives with arenethiol as the hydrogen atom transfer catalyst making UAAs peptides. The formate salt, acting donor, situ generates reductive CO

Язык: Английский

Процитировано

2