Herein, we report a novel intramolecular ring-closing reaction of biaryl thioethers that give access to highly functionalized dibenzothiophene sulfonium salts under mild conditions. The resulting precursors react regioselectively with [F]fluoride to give [F]fluoroarenes in predictable radiochemical yields. The strategy expands the available radiochemical space and provides superior labeling efficiency for clinically relevant PET tracers.
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http://dx.doi.org/10.1021/jacs.8b06730 | DOI Listing |
Chem Sci
April 2024
Institut für Organische und Biomolekulare Chemie, Georg August Universität Göttingen Tammannstr 2 37077 Göttingen Germany
In the presence of catalytic amounts of the paddlewheel dirhodium complex Rh(esp), α-diazo dibenzothiophenium salts generate highly electrophilic Rh-coordinated carbenes, which evolve differently depending on their substitution pattern. Keto-moieties directly attached to the azomethinic carbon promote carbene insertion into one of the adjacent C-S bonds, giving rise to highly electrophilic dibenzothiopyrilium salts. This intramolecular pathway is not operative when the carbene carbon bears ester or trifluoromethyl substituents; in fact, these species react with olefins delivering easy to handle cyclopropyl-substituted sulfonium salts.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
June 2024
Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstr. 2, D-37077, Göttingen, Germany.
The one-pot synthesis of λ-dibenzothiophen-5-imino-N-dibenzothiophenium triflate (1) in multigram scale is reported. This compound reacts with Rh(esp) (esp=α,α,α',α'-tetramethyl-1,3-benzenedipropionic acid) generating a Rh-coordinated sulfonitrene species, which is able to transfer the electrophilic nitrene moiety to olefins. When indenes are used as substrates, isoquinolines are obtained in good yields.
View Article and Find Full Text PDFTalanta
February 2024
A.V.Topchiev Institute of Petrochemical Synthesis of the Russian Academy of Sciences, 29 Leninskiy Prosp., Moscow, 119991, Russian Federation.
This paper describes rather suitable and variable preliminary derivatization strategy that may precede the molecular level characterization of sulfur-containing compounds of a particularly aromatic nature by high-resolution MALDI and ESI mass spectrometry. We demonstrated for the first time that free aliphatic alcohols (primary 1-alkanols C3-C20) in the presence of triflic acid provide easy S-alkylation of not only saturated sulfides but also most typical aromatic sulfur-containing compounds (benzothiophene, dibenzothiophene and their homologues) widely distributed and frequently analyzed in oil. The reaction proceeds quantitatively at rather mild conditions and gives rise to corresponding S-alkyl sulfonium salts the cation moieties of which can be detected using MALDI and ESI mass spectrometry with excellent signal/noise (S/N) ratios; the response ratios for target ions being quite close for both methods.
View Article and Find Full Text PDFInorg Chem
August 2023
School of Chemical Sciences, Indian Institute of Technology Mandi, Kamand 175005, Himachal Pradesh, India.
Multifunctional materials based on polyoxovanadates (POVs) have rarely been reported. Herein, we used aryl sulfonium counterions (ASCIs) bearing a salicylaldehyde-type functionality to tune the properties of decavanadate ([VO])-based hybrids for their application in photochromism and heterogeneous oxidative desulfurization (ODS) catalysis. The counterions FHPDS ((3-formyl-4-hydroxyphenyl)dimethylsulfonium), DFHPDS ((3,5-diformyl-4-hydroxyphenyl)dimethylsulfonium), and EFPDS ((4-ethoxy-3-formylphenyl)dimethylsulfonium) were clubbed with the decavanadate cluster to generate the hybrids (FHPDS)[HVO](HO) (), (DFHPDS)[HVO](HO) (), and (EFPDS)[HVO](HO) ().
View Article and Find Full Text PDFMolecules
December 2022
A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninskiy Prosp., 119991 Moscow, Russia.
Polycyclic aromatic sulfur-containing compounds are widely distributed in oil, especially in its low-volatile and heavy fractions (resins, asphaltenes), and this dictates the need for their determination when reliable methods for sulfur removing, cleaning and processing oil are developed. In these cases, "soft" ionization mass spectrometry methods, based on electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI), are particularly effective. However, aromatic sulfur-containing compounds have low polarity and cannot be readily ionized by these methods.
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