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Keywords = stannylation

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10 pages, 1473 KB  
Article
Coupling Pyrazine to Dithiocarbonates for Molybdopterin Model Ligands—Indispensable Tin
by Siva Sankar Murthy Bandaru, Claudia Schindler, Felix Wenzek and Carola Schulzke
Inorganics 2023, 11(5), 188; https://doi.org/10.3390/inorganics11050188 - 26 Apr 2023
Viewed by 2362
Abstract
Several synthetic cross-coupling procedures were (re-)evaluated for the tethering of pyrazine to dithiocarbonates. The resultant species constitute pro-ligands and can be converted by removal of the C=O moiety into ene-dithiolate ligand systems that model molybdopterin. The coupling of 2-iodopyrazine with the stannylated dithiocarbonate [...] Read more.
Several synthetic cross-coupling procedures were (re-)evaluated for the tethering of pyrazine to dithiocarbonates. The resultant species constitute pro-ligands and can be converted by removal of the C=O moiety into ene-dithiolate ligand systems that model molybdopterin. The coupling of 2-iodopyrazine with the stannylated dithiocarbonate units mediated by copper(I)-thiophene-2-carboxylate in stoichiometric equivalents proved to be the most efficient and the only reliable route to the targeted compounds. Single-crystal X-ray structural analysis confirmed the final structures of two pursued pyrazine-derived dithiocarbonates and those of two intermediates. Full article
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12 pages, 1803 KB  
Article
Effective Preparation of [18F]Flumazenil Using Copper-Mediated Late-Stage Radiofluorination of a Stannyl Precursor
by Mohammad B. Haskali, Peter D. Roselt, Terence J. O’Brien, Craig A. Hutton, Idrish Ali, Lucy Vivash and Bianca Jupp
Molecules 2022, 27(18), 5931; https://doi.org/10.3390/molecules27185931 - 13 Sep 2022
Cited by 8 | Viewed by 3889
Abstract
(1) Background: [18F]Flumazenil 1 ([18F]FMZ) is an established positron emission tomography (PET) radiotracer for the imaging of the gamma-aminobutyric acid (GABA) receptor subtype, GABAA in the brain. The production of [18F]FMZ 1 for its clinical use [...] Read more.
(1) Background: [18F]Flumazenil 1 ([18F]FMZ) is an established positron emission tomography (PET) radiotracer for the imaging of the gamma-aminobutyric acid (GABA) receptor subtype, GABAA in the brain. The production of [18F]FMZ 1 for its clinical use has proven to be challenging, requiring harsh radiochemical conditions, while affording low radiochemical yields. Fully characterized, new methods for the improved production of [18F]FMZ 1 are needed. (2) Methods: We investigate the use of late-stage copper-mediated radiofluorination of aryl stannanes to improve the production of [18F]FMZ 1 that is suitable for clinical use. Mass spectrometry was used to identify the chemical by-products that were produced under the reaction conditions. (3) Results: The radiosynthesis of [18F]FMZ 1 was fully automated using the iPhase FlexLab radiochemistry module, affording a 22.2 ± 2.7% (n = 5) decay-corrected yield after 80 min. [18F]FMZ 1 was obtained with a high radiochemical purity (>98%) and molar activity (247.9 ± 25.9 GBq/µmol). (4) Conclusions: The copper-mediated radiofluorination of the stannyl precursor is an effective strategy for the production of clinically suitable [18F]FMZ 1. Full article
(This article belongs to the Special Issue Radiopharmaceuticals)
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17 pages, 2498 KB  
Article
Highly Diastereoselective Chelation-Controlled 1,3-anti-Allylation of (S)-3-(Methoxymethyl)hexanal Enabled by Hydrate of Scandium Triflate
by Uladzimir S. Masiuk, Iryna V. Mineyeva and Dzmitry G. Kananovich
Symmetry 2021, 13(3), 470; https://doi.org/10.3390/sym13030470 - 13 Mar 2021
Cited by 10 | Viewed by 6287
Abstract
En route to the total synthesis of (+)-Neopeltolide, we explored Lewis acid-assisted diastereoselective allylation of MOM-protected 3-hydroxylhexanal with β-(2,2-diethoxyethyl)-substituted (allyl)tributylstannane. The hydrated form of scandium triflate was found to be essential for attaining high 1,3-anti-diastereoselectivity (d.r. 94:6), while the use of [...] Read more.
En route to the total synthesis of (+)-Neopeltolide, we explored Lewis acid-assisted diastereoselective allylation of MOM-protected 3-hydroxylhexanal with β-(2,2-diethoxyethyl)-substituted (allyl)tributylstannane. The hydrated form of scandium triflate was found to be essential for attaining high 1,3-anti-diastereoselectivity (d.r. 94:6), while the use of anhydrous catalyst resulted in a modest diastereocontrol (d.r. 76:24). The preferred 1,3-anti-selectivity in this transformation can be rationalized in the framework of the Reetz chelate model of asymmetric induction. The 1,3-anti-configuration of the product was confirmed by its conversion into the known C7-C16 building block of (+)-Neopeltolide. We also report an improved protocol for the synthesis of β-(2,2-diethoxyethyl)-substituted (allyl)tributylstannane, which can be utilized as a cost-efficient bipolar isoprenoid-type C5-building block in the synthesis of natural compounds. Full article
(This article belongs to the Special Issue Chirality and Symmetry in Stereochemistry)
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11 pages, 4561 KB  
Article
Nickel-Catalyzed Decarbonylative Stannylation of Acyl Fluorides under Ligand-Free Conditions
by Xiu Wang, Zhenhua Wang, Li Liu, Yuya Asanuma and Yasushi Nishihara
Molecules 2019, 24(9), 1671; https://doi.org/10.3390/molecules24091671 - 28 Apr 2019
Cited by 37 | Viewed by 6409
Abstract
Nickel-catalyzed decarbonylative stannylation of acyl fluorides under ligand-free conditions was disclosed. A variety of aromatic acyl fluorides are capable of reacting with silylstannanes in the presence of cesium fluoride. A one-pot decarbonylative stannylation/Migita-Kosugi-Stille reaction of benzoyl fluoride, giving rise to the direct formation [...] Read more.
Nickel-catalyzed decarbonylative stannylation of acyl fluorides under ligand-free conditions was disclosed. A variety of aromatic acyl fluorides are capable of reacting with silylstannanes in the presence of cesium fluoride. A one-pot decarbonylative stannylation/Migita-Kosugi-Stille reaction of benzoyl fluoride, giving rise to the direct formation of the corresponding cross-coupled products, further demonstrated the synthetic utility of the present method. This newly developed methodology with a good functional-group compatibility via C–F bond cleavage and C–Sn bond formation under nickel catalysis opens a new area for the functionalization of acyl fluorides in terms of carbon-heteroatom bond formation. Full article
(This article belongs to the Special Issue Nickel Complexes for Catalysis)
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19 pages, 30765 KB  
Article
Synthesis, Structure, Thermal Behavior and cis/trans Isomerization of 2,2′-(EMe3)2 (E = C, Si, Ge, Sn) Substituted Azobenzenes
by Jonas Hoffmann, Thomas Josef Kuczmera, Enno Lork and Anne Staubitz
Molecules 2019, 24(2), 303; https://doi.org/10.3390/molecules24020303 - 15 Jan 2019
Cited by 7 | Viewed by 6730
Abstract
The synthesis of a series of 2,2′-bis(trimethyltetrel) azobenzenes is reported, evaluating the different synthetic approaches that different group 14 element substituents individually require. The synthetic access to the carbon substituted congener is very different from the heavier tetrels, in that the key step [...] Read more.
The synthesis of a series of 2,2′-bis(trimethyltetrel) azobenzenes is reported, evaluating the different synthetic approaches that different group 14 element substituents individually require. The synthetic access to the carbon substituted congener is very different from the heavier tetrels, in that the key step is the formation of the N=N bond in azobenzene, rather than the azobenzene-C bond. Sn could be introduced with a cross-coupling route, whereas the Si and Ge congeners were prepared by a stannylation-lithiation-electrophilic quenching sequence. Iodo-lithium exchange was also a possible route to obtain the dilithiated species, which can be attributed to the chelating effect of the nitrogen atoms. However, the organo-lead species could not be obtained via these routes. The resulting structures were fully characterized (NMR, FTIR, HRMS and XRD). Furthermore, their thermal properties (TGA and DSC) and their photoswitching behavior in solution (UV-VIS & NMR experiments) were investigated and compared for the different tetrels (C, Si, Ge, Sn). Full article
(This article belongs to the Special Issue Main Group Elements in Synthesis)
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25 pages, 5042 KB  
Article
A Practical Method for the Preparation of 18F-Labeled Aromatic Amino Acids from Nucleophilic [18F]Fluoride and Stannyl Precursors for Electrophilic Radiohalogenation
by Fadi Zarrad, Boris D. Zlatopolskiy, Philipp Krapf, Johannes Zischler and Bernd Neumaier
Molecules 2017, 22(12), 2231; https://doi.org/10.3390/molecules22122231 - 15 Dec 2017
Cited by 43 | Viewed by 9734
Abstract
In a recent contribution of Scott et al., the substrate scope of Cu-mediated nucleophilic radiofluorination with [18F]KF for the preparation of 18F-labeled arenes was extended to aryl- and vinylstannanes. Based on these findings, the potential of this reaction for the [...] Read more.
In a recent contribution of Scott et al., the substrate scope of Cu-mediated nucleophilic radiofluorination with [18F]KF for the preparation of 18F-labeled arenes was extended to aryl- and vinylstannanes. Based on these findings, the potential of this reaction for the production of clinically relevant positron emission tomography (PET) tracers was investigated. To this end, Cu-mediated radiofluorodestannylation using trimethyl(phenyl)tin as a model substrate was re-evaluated with respect to different reaction parameters. The resulting labeling protocol was applied for 18F-fluorination of different electron-rich, -neutral and -poor arylstannyl substrates in RCCs of 16–88%. Furthermore, this method was utilized for the synthesis of 18F-labeled aromatic amino acids from additionally N-Boc protected commercially available stannyl precursors routinely applied for electrophilic radiohalogenation. Finally, an automated synthesis of 6-[18F]fluoro-l-m-tyrosine (6-[18F]FMT), 2-[18F]fluoro-l-tyrosine (2-[18F]F-Tyr), 6-[18F]fluoro-l-3,4-dihydroxyphenylalanine (6-[18F]FDOPA) and 3-O-methyl-6-[18F]FDOPA ([18F]OMFD) was established furnishing these PET probes in isolated radiochemical yields (RCYs) of 32–54% on a preparative scale. Remarkably, the automated radiosynthesis of 6-[18F]FDOPA afforded an exceptionally high RCY of 54 ± 5% (n = 5). Full article
(This article belongs to the Section Medicinal Chemistry)
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13 pages, 2095 KB  
Article
Synthesis and In Vitro (Anticancer) Evaluation of η6-Arene Ruthenium Complexes Bearing Stannyl Ligands
by Olivier Renier, Connor Deacon-Price, Joannes E. B. Peters, Kunsulu Nurekeyeva, Catherine Russon, Simba Dyson, Siyabonga Ngubane, Judith Baumgartner, Paul J. Dyson, Tina Riedel, Haleden Chiririwa and Burgert Blom
Inorganics 2017, 5(3), 44; https://doi.org/10.3390/inorganics5030044 - 13 Jul 2017
Cited by 16 | Viewed by 7574
Abstract
Treatment of the known half-sandwich complexes of the type [(η6-C6H6)RuCl2(P(OR)3)] (R = Me or Ph) with SnCl2 yielded three new half-sandwich ruthenium complexes (C1C3): [(η6-C6 [...] Read more.
Treatment of the known half-sandwich complexes of the type [(η6-C6H6)RuCl2(P(OR)3)] (R = Me or Ph) with SnCl2 yielded three new half-sandwich ruthenium complexes (C1C3): [(η6-C6H6)RuCl(SnCl3)(P(OMe)3)] (C1), [(η6-C6H6)RuCl(SnCl3)(P(OPh)3)] (C2) and the bis-stannyl complex [(η6-C6H6)Ru(SnCl3)2(P(OMe)3)] (C3) by facile insertion of SnCl2 into the Ru–Cl bonds. Treatment of the known complexes [(η6-C6H6)RuCl(SnCl3)(PPh3)] and [(η6-C6H6)RuCl2(PPh3)] with 4-dimethylaminopyridine (DAMP) and ammonium tetrafluoroborate afforded the complex salts: [(η6-C6H6)Ru(SnCl3)(PPh3)(DAMP)]+BF4 (C4) and [(η6-C6H6)RuCl(PPh3)(DAMP)]+BF4 (C5) respectively. Complexes C1C5 have been fully characterized by spectroscopic means (IR, UV–vis, multinuclear NMR, ESI–MS) and their thermal behaviour elucidated by thermal gravimetric analysis (TGA). Structural characterization by single crystal X-ray crystallography of the novel complex C2 and [(η6-C6H6)RuCl2(P(OPh)3)], the latter having escaped elucidation by this method, is also reported. Finally, the cytotoxicity of the complexes was determined on the A2780 (human ovarian cancer), A2780cisR (human ovarian cis-platin-resistant cancer), and the HEK293 (human embryonic kidney) cell lines and discussed, and an attempt is made to elucidate the effect of the stannyl ligand on cytotoxicity. Full article
(This article belongs to the Special Issue Tumor Inhibiting Metal Complexes)
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15 pages, 459 KB  
Review
Fluorinated Poly(p-phenylenevinylene)s: Synthesis and Optical Properties of an Intriguing Class of Luminescent Polymers
by Gianluca M. Farinola, Antonio Cardone, Francesco Babudri, Carmela Martinelli, Francesco Naso, Giovanni Bruno and Maria Losurdo
Materials 2010, 3(5), 3077-3091; https://doi.org/10.3390/ma3053077 - 7 May 2010
Cited by 30 | Viewed by 13421
Abstract
This review is an overview of our previous work on the synthesis and properties of poly(p-phenylenevinylene)s (PPVs) selectively fluorinated in different positions of the conjugated backbone. Both the synthetic challenges and the effects of functionalization with fluorine atoms on the optical [...] Read more.
This review is an overview of our previous work on the synthesis and properties of poly(p-phenylenevinylene)s (PPVs) selectively fluorinated in different positions of the conjugated backbone. Both the synthetic challenges and the effects of functionalization with fluorine atoms on the optical behavior are discussed, highlighting the peculiarities and the interest of this class of conjugated polymers. A general polymerization protocol for PPVs, that is based on the Pd-catalyzed Stille cross-coupling reaction of bis-stannylated vinylene monomers with aromatic bis-halides, has been successfully extended to the synthesis of selectively fluorinated poly(p-phenylenevinylene)s. The properties of a series of these PPVs differing in the number and positions of the fluorine atoms on the conjugated backbone have been studied, even in comparison with the non-fluorinated counterparts. The intriguing optical features of the resulting materials are discussed considering not only the role of the electronic and steric effects induced by the fluorine substituents, but also the impact of the fluorination on the solid state organization and intermolecular interactions. Full article
(This article belongs to the Special Issue Organic Electronic Materials)
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12 pages, 65 KB  
Review
Recent Advances in the Substitution Reactions of Triorganylstannyl Ions with Aromatic Compounds by the SRN1 Mechanism. Synthetic Applications
by Eduardo F. Córsico, Al Postigo and Roberto A. Rossi
Molecules 2000, 5(9), 1068-1079; https://doi.org/10.3390/50901068 - 11 Sep 2000
Cited by 3 | Viewed by 11327
Abstract
A review on the reactions of triorganyl stannyl ions with haloarenes is presented. Emphasis on the synthetic applications of the resulting triorganyl stannyl aryl compounds is made, with their inherent potential to build large molecules through the SRN1 sequence, i.e. ArX→ArSnR [...] Read more.
A review on the reactions of triorganyl stannyl ions with haloarenes is presented. Emphasis on the synthetic applications of the resulting triorganyl stannyl aryl compounds is made, with their inherent potential to build large molecules through the SRN1 sequence, i.e. ArX→ArSnR3→ArAr, which can be iteratively repeated when appropriately substituted substrates are chosen. Full article
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Scheme 1

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