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15 pages, 1744 KB

Open AccessArticle

New Conjugatable Platinum(II) Chlorins: Synthesis, Reactivity and Singlet Oxygen Generation

by José Almeida, Giampaolo Barone, Luís Cunha-Silva, Ana F. R. Cerqueira, Augusto C. Tomé, Maria Rangel and Ana M. G. Silva

Molecules 2025, 30(12), 2496; https://doi.org/10.3390/molecules30122496 - 6 Jun 2025

Viewed by 461

Abstract

An efficient protocol was developed for the microwave-mediated metallation of 5-(4-methoxycarbonylphenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (P1) with bis(benzonitrile)platinum dichloride salt and subsequent 1,3-dipolar cycloaddition of the resulting PtP1 with an azomethine ylide to give two isomeric metallochlorins: PtC1 (main isomer) and PtC3. The methyl ester group of metalloporphyrin PtP1 and metallochlorin PtC1 was successfully hydrolysed in an alkaline medium to yield the corresponding derivatives PtP2 and PtC2 in moderate-to-good yields. As a proof of concept of the reactivity of the carboxy group in PtP2 and PtC2, these compounds were conjugated with a hydroxylated derivative of indomethacin, a known potent non-steroidal anti-inflammatory, obtaining the conjugates PtP2-Ind and PtC2-Ind. The obtained platinum(II) porphyrins and chlorins were characterized by UV-Vis, NMR spectroscopy and mass spectrometry. The structure of PtP1 was also confirmed by X-ray crystallography. Singlet oxygen generation studies were carried out, as well as theoretical calculations, which demonstrated that the prepared Pt(II) complexes can be considered potential photosensitizers for PDT. Full article

(This article belongs to the Section Colorants)

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10 pages, 2657 KB

Open AccessArticle

New Insight into the Reactivity of S,S-Bis-ylide

by Ugo Authesserre, V. S. V. S. N. Swamy, Nathalie Saffon-Merceron, Antoine Baceiredo, Tsuyoshi Kato and Eddy Maerten

Molecules 2023, 28(8), 3295; https://doi.org/10.3390/molecules28083295 - 7 Apr 2023

Cited by 2 | Viewed by 2742

Abstract

The present work focuses on the reactivity of S,S-bis-ylide 2, which presents a strong nucleophilic character, as evidenced by reactions with methyl iodide and CO₂, affording C-methylated salts 3 and betaine 4, respectively. The derivatization of betaine 4 affords the corresponding ester derivative 6, which is fully characterized by using NMR spectroscopy and X-ray diffraction analysis. Furthermore, an original reaction with phosphenium ions leads to the formation of a transient push–pull phosphino(sulfonio)carbene 8, which rearranges to give stabilized sulfonium ylide derivative 7. Full article

(This article belongs to the Special Issue Feature Papers in Organic Chemistry (Volume II))

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14 pages, 4256 KB

Open AccessArticle

Oxo-Stabilised Phosphonium Ylides as Hydrogen Bond Acceptors

by R. Alan Aitken, Lee P. Cleghorn, Graham Dawson, Ian P. Gray, Anna Lashtabeg and Alexandra M. Z. Slawin

Inorganics 2023, 11(2), 50; https://doi.org/10.3390/inorganics11020050 - 18 Jan 2023

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Abstract

Oxo-stabilised phosphonium ylides are found to form crystalline hydrogen-bonded adducts with aromatic carboxylic acids, as confirmed by X-ray diffraction. There is also strong hydrogen bonding in solution as indicated by ¹³C NMR spectroscopy and this confirmed adduct formation with acetic acid, benzamide, thiobenzamide, benzyl alcohol, benzenesulfinic acid and diphenylphosphinic acid. The X-ray structure of the benzamide adduct was also determined, showing a hydrogen-bonded dimeric structure. A bis(stabilised ylide) was also prepared and is found to form a complex hydrogen-bonded adduct with benzoic acid, ethanol and water. Full article

(This article belongs to the Special Issue Bond Activation and Catalysis Using Main-Group Elements)

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18 pages, 5346 KB

Open AccessArticle

Straightforward Regio- and Diastereoselective Synthesis, Molecular Structure, Intermolecular Interactions and Mechanistic Study of Spirooxindole-Engrafted Rhodanine Analogs

by Assem Barakat, Matti Haukka, Saied M. Soliman, M. Ali, Abdullah Mohammed Al-Majid, Ayman El-Faham and Luis R. Domingo

Molecules 2021, 26(23), 7276; https://doi.org/10.3390/molecules26237276 - 30 Nov 2021

Cited by 14 | Viewed by 3660

Abstract

Straightforward regio- and diastereoselective synthesis of bi-spirooxindole-engrafted rhodanine analogs 5a–d were achieved by one-pot multicomponent [3 + 2] cycloaddition (32CA) reaction of stabilized azomethine ylide (AYs 3a–d) generated in situ by condensation of L-thioproline and 6-chloro-isatin with (E)-2-(5-(4-chlorobenzylidene)-2,4-dioxothiazolidin-3-yl)-N-(2-morpholinoethyl)acetamide. The bi-spirooxindole-engrafted rhodanine analogs were constructed with excellent diastereo- and regioselectivity along with high chemical yield. X-ray crystallographic investigations for hybrid 5a revealed the presence of four contiguous stereocenters related to C11, C12, C19 and C22 of the spiro structure. Hirshfeld calculations indicated the presence of many short intermolecular contacts such as Cl...C, S...S, S...H, O...H, N...H, H...C, C...C and H...H interactions. These contacts played a very important role in the crystal stability. The polar nature of the 32CA reaction was studied by analysis of the conceptual DFT reactivity indices. Theoretical study of this 32CA reaction indicated that it takes place through a non-concerted two-stage one-step mechanism associated with the nucleophilic attack of AY 3a to the electrophilic ethylene derivative. Full article

(This article belongs to the Section Computational and Theoretical Chemistry)

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9 pages, 1584 KB

Open AccessArticle

Complexes of Dichlorogermylene with Phosphine/Sulfoxide-Supported Carbone as Ligand

by Ugo Authesserre, Sophie Hameury, Aymeric Dajnak, Nathalie Saffon-Merceron, Antoine Baceiredo, David Madec and Eddy Maerten

Molecules 2021, 26(7), 2005; https://doi.org/10.3390/molecules26072005 - 1 Apr 2021

Cited by 4 | Viewed by 2811

Abstract

Due to their remarkable electronic features, recent years have witnessed the emergence of carbones L₂C, which consist in two donating L ligands coordinating a central carbon atom bearing two lone pairs. In this context, the phosphine/sulfoxide-supported carbone 4 exhibits a strong nucleophilic character, and here, we describe its ability to coordinate dichlorogermylene. Two original stable coordination complexes were obtained and fully characterized in solution and in the solid state by NMR spectroscopy and X-ray diffraction analysis, respectively. At 60 °C, in the presence of 4, the Ge(II)-complex 5 undergoes a slow isomerization that transforms the bis-ylide ligand into an yldiide. Full article

(This article belongs to the Special Issue Carbon Ligands: From Fundamental Aspects to Applications)

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9 pages, 1082 KB

Open AccessArticle

[Bmim]Br Accelerated One-Pot Three-Component Cascade Protocol for the Construction of Spirooxindole–Pyrrolidine Heterocyclic Hybrids

by Raju Suresh Kumar, Dhaifallah M. Al-thamili, Abdulrahman I. Almansour, Natarajan Arumugam and Necmi Dege

Molecules 2020, 25(20), 4779; https://doi.org/10.3390/molecules25204779 - 18 Oct 2020

Cited by 8 | Viewed by 2527

Abstract

Our synthetic approach for the assembly of structurally complex spirooxindole heterocyclic hybrids was based on an ionic liquid, [bmim]Br mediated one-pot three-component cascade reaction strategy involving 1,3-dipolar cycloaddition reaction of N-1-(2-pyridinylmethyl)-3,5-bis[(E)-arylmethylidene]tetrahydro-4(1H)-pyridinones and azomethine ylide generated in situ from isatin and L-phenyl alanine, affording a series of spirooxindole–pyrrolidine heterocyclic hybrids in good-to-excellent yields. In addition to serving as the reaction medium, [bmim]Br also functioned as a catalyst in this cycloaddition reaction and hence accelerated the reaction rate affording the cycloadducts in short reaction time. Full article

(This article belongs to the Special Issue Recent Advances in Cascade Reactions and Related One-Pot Processes)

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23 pages, 594 KB

Open AccessArticle

Facile, Regio- and Diastereoselective Synthesis of Spiro-Pyrrolidine and Pyrrolizine Derivatives and Evaluation of Their Antiproliferative Activities

by Abdulrahman I. Almansour, Raju Suresh Kumar, Farzana Beevi, Amir Nasrolahi Shirazi, Hasnah Osman, Rusli Ismail, Tan Soo Choon, Brian Sullivan, Kellen McCaffrey, Alaa Nahhas, Keykavous Parang and Mohamed Ashraf Ali

Molecules 2014, 19(7), 10033-10055; https://doi.org/10.3390/molecules190710033 - 10 Jul 2014

Cited by 42 | Viewed by 7509

Abstract

A number of novel spiro-pyrrolidines/pyrrolizines derivatives were synthesized through [3+2]-cycloaddition of azomethine ylides with 3,5-bis[(E)-arylmethylidene]tetrahydro-4(1H)-pyridinones 2a–n. Azomethine ylides were generated in situ from the reaction of 1H-indole-2,3-dione (isatin, 3) with N-methylglycine (sarcosine), phenylglycine, or proline. All compounds (50 μM) were evaluated for their antiproliferative activity against human breast carcinoma (MDA-MB-231), leukemia lymphoblastic (CCRF-CEM), and ovarian carcinoma (SK-OV-3) cells. N-α-Phenyl substituted spiro-pyrrolidine derivatives (5a–n) showed higher antiproliferative activity in MDA-MB-231 than other cancer cell lines. Among spiro-pyrrolizines 6a–n, a number of derivatives including 6a–c and 6i–m showed a comparable activity with doxorubicin in all three cell lines. Among all compounds in three classes, 6a, 6b, and 6m, were found to be the most potent derivatives showing 64%, 87%, and 74% antiproliferative activity in MDA-MB-231, SK-OV-3, and CCRF-CEM cells, respectively. Compound 6b showed an IC₅₀ value of 3.6 mM in CCRF-CEM cells. These data suggest the potential antiproliferative activity of spiro-pyrrolidines/pyrrolizines. Full article

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