Copper Photocatalyzed Divergent Access to Organic Thio- and Isothiocyanates

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 4847 - 4855

Опубликована: Март 16, 2024

We disclose a copper-photocatalyzed strategy that enables selective access to organic thiocyanates and isothiocyanates using benzylic as ATRA reagents. The electronic nature of the aromatic system is crucial factor defining outcome reaction for forging either kinetic C–S or thermodynamic C–N bonds. Mechanistic investigations support radical pathway initiated by reductive bond cleavage substrates followed divergent inner-/outer-sphere interaction with copper depending on density formed intermediates. developed protocol proceeds high regio- chemoselectivity can also be applied late-stage functionalization bioactive molecules. utility products highlighted their facile conversion several building blocks are relevant synthesis.

Язык: Английский

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Switchable Nucleophilic Site Enables Expedient Synthesis of CF₃-Containing Thiazoles and Allenes from 1,3-Enynes

ACS Catalysis, Год журнала: 2023, Номер 13(19), С. 12755 - 12765

Опубликована: Сен. 15, 2023

Typically, trimethylsilyl isothiocyanate (TMSNCS) is used as a nucleophilic thiocyanate building block (−S–C≡N) that reacts with various electrophiles. However, it has been less explored source of isothiocyanates (−N═C═S), which can usually be converted by thermal isomerization allyl or propargyl thiocyanates. Achieving method precise site control even more challenging. Here, we demonstrate an approach uses metal catalysts to switchable sites and provide strategy construct CF3-containing thiazoles allenes via the multicomponent reaction 1,3-enynes, TMSNCS, electrophilic trifluoromethyl reagent. In presence inexpensive Fe(III) Cu(II) catalysts, current practical convenient, compatible substrates bearing sensitive functional groups readily transferred complex scaffolds. The biological evaluation showed two developed exhibited dramatic inhibitory activities for three human cancer cell lines beyond those 5-fluorouracil. Both compounds increased level reactive oxygen species in MCF-7 cells, believed early step tumor apoptosis.

Язык: Английский

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Biofortification of health-promoting glucosinolates in cruciferous sprouts along the whole agro-food chain

Trends in Food Science & Technology, Год журнала: 2023, Номер 140, С. 104164 - 104164

Опубликована: Сен. 2, 2023

Язык: Английский

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Discovery of Novel Pyrazol-5-yl-benzamide Derivatives Containing a Thiocyanato Group as Broad-Spectrum Fungicidal Candidates

Journal of Agricultural and Food Chemistry, Год журнала: 2023, Номер 71(46), С. 17700 - 17712

Опубликована: Ноя. 8, 2023

In an effort to promote the development of new fungicides, a series 48 novel N-(1-methyl-4-thiocyanato-1H-pyrazol-5-yl)-benzamide derivatives A1-A36 and B1-B12 were designed synthesized by incorporating thiocyanato group into pyrazole ring, their fungicidal activities evaluated against Sclerotinia sclerotiorum, Valsa mali, Botrytis cinerea, Rhizoctonia solani, Phytophthora capsici. in vitro antifungal/antioomycete assay, many target compounds exhibited good broad-spectrum activities. Among them, compound A36 displayed best antifungal activity V. mali with EC50 value 0.37 mg/L, which was significantly higher than that positive controls fluxapyroxad (13.3 mg/L) dimethomorph (10.3 mg/L). Meanwhile, B6 antioomycete P. capsici 0.41 azoxystrobin (29.2 but lower (0.13 Notably, A27 inhibitory B. R. S. respective values 0.71, 1.44, 1.78, 0.87, 1.61 mg/L. The vivo experiments revealed presented excellent protective curative efficacies capsici, similar control dimethomorph. Scanning electron microscopy (SEM) transmission (TEM) analyses showed could change mycelial morphology severely damage ultrastructure results SDH enzymatic inhibition indicated effectively inhibit (PcSDH). Furthermore, molecular docking analysis demonstrated significant hydrogen bonds Pi-S bonding between key amino acid residues PcSDH, explain probable mechanism action. Collectively, these studies provide valuable approach expanding spectrum pyrazol-5-yl-benzamide derivatives.

Язык: Английский

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Electrochemical remote C(sp³)–H thiocyanation

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(8), С. 2283 - 2288

Опубликована: Янв. 1, 2024

An electrochemical thiocyanation of distal C(sp 3 )–H bonds based on amidyl radical-mediated 1,5-HAT has been developed. The transformation is highly site-selective and compatible with primary, secondary, tertiary sulfonamides, bioactive derivatives.

Язык: Английский

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Carbene-induced ring-opening reactions of five-/six-membered cyclic ethers: expanding the frontiers of functional group introduction and molecular architecture construction

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

The multi-component ring-opening reactions of cyclic ethers offer an efficient strategy for the rapid introduction multiple functional groups and construction complex molecular architectures.

Язык: Английский

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Modern tools for the functionalization of C(sp3) centers by catalysis

Comptes Rendus Chimie, Год журнала: 2025, Номер 28(G1), С. 27 - 35

Опубликована: Фев. 13, 2025

In the quest for molecular complexity, direct and selective functionalization of C(sp3) centers is paramount importance. As sulfur- and/or fluorine-containing molecules are particularly important, development methods to (regio)selectively introduce moieties containing these atoms on a center by C–H bond or decarboxylative reaction has garnered our interest in last few years. Given challenges that represents, this account summarizes recent contributions thanks strategies based transition metal catalysis photochemistry. La fonctionnalisation directe et sélective de centres est une approche remarquable permettant d'obtenir des molécules complexes façon efficace. Du fait l'importance contenant du soufre et/ou fluor, le développement méthodes pour introduire (régio)sélectivement groupements ces atomes sur un centre C(sp3), par d'une liaison ou réaction décarboxylante, suscité vif intérêt au cours dernières années. Étant donné les défis que représente la cet article résume nos récentes grâce à stratégies basées catalyse métaux photochimie.

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Copper‐Catalyzed 1,5‐Trifluoromethyl‐thio(seleno)cyanation of 5‐Hexenenitriles with an Intramolecular Cyano Migration

Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown

Опубликована: Март 12, 2025

Abstract A copper‐catalyzed remote 1,5‐trifluoromethyl thio(seleno)cyanation of 5‐hexenenitriles with an intramolecular cyano migration has been established, affording a variety CF 3 /CN‐containing thiocyanates and selenocyanates under mild conditions. The reaction features high chemo‐ regioselectivities illustrates potential value in synthetic chemistry.

Язык: Английский

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Selective C(sp2) –H Bond Radical Thiocyanation of Cyclic α, β-Unsaturated Ketones

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This paper reports an AIBN-initiated radical thiocyanation reaction of alkenes, which efficiently achieves the conjugated unsaturated alkenes such as uracils and quinolinones.

Язык: Английский

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Visible-light-induced aerobic C-3 thiocyanation of indoles using carbon dots as photoredox catalyst

Tetrahedron Letters, Год журнала: 2025, Номер 160, С. 155545 - 155545

Опубликована: Март 15, 2025

Язык: Английский

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