In this article, a high-yield method for the synthesis of sulfonyl 9-fluorenylidenes is described, which consists of a one-pot straightforward three-step synthetic route, including (i) CuBr-mediated α-bromination of -arylacetophenone, (ii) sequential nucleophilic substitution of the resulting α-bromo -arylacetophenone with sodium sulfinate (RSONa), and (iii) the CuBr-mediated intramolecular Friedel-Crafts cyclizative dehydration. A plausible mechanism is proposed and discussed. This protocol provides a highly effective regio- and stereoselective annulation via the formation of one carbon-carbon (C-C) bond and one carbon-sulfur (C-S) bond.
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http://dx.doi.org/10.1021/acs.joc.0c00035 | DOI Listing |
J Org Chem
December 2024
College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, Zhejiang, China.
In this work, a switchable synthesis of β-ketosulfone and α-chloroketone through a radical difunctionalization of alkenes is reported. The transformation works well under iron peroxo species/photoredox dual catalysis and an open-flask atmosphere, and the reaction is highlighted with good yields and a broad reaction scope. Mechanism studies show that the reaction is initiated by a formal [4 + 2] cyclization of the sulfonyl radical in a regioselective manner.
View Article and Find Full Text PDFOrg Lett
December 2024
Organic Chemistry Department, Science Faculty, Patrice Lumumba Peoples' Friendship University of Russia (RUDN University), Miklukho-Maklaya strasse, 6, 117198 Moscow, Russia.
Electrolysis of -alkynyl--(formyl)anilides and sodium sulfinates on graphite electrodes delivers biologically sound 3-(sulfonyl)quinol-4-ones with moderate to good yields. The reaction is carried out in an undivided cell in the presence of silver(I) oxide with potassium iodide or sodium tetrafluoroborate as the supporting electrolyte. The reaction tolerates variously substituted anilides as well as aryl and alkyl sulfinates.
View Article and Find Full Text PDFOrg Lett
December 2024
Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan, Hunan 411105, China.
We herein report a photochemical Truce-Smiles rearrangement reaction of -sulfinyl acrylamides with bromodifluoroacetamides resulting in the synthesis of a series of aryl difluoroglutaramides in moderate to good yields. The asymmetric synthesis using chiral sulfinamides produced quaternary carboncentered glutaramide products with a modest enantioselectivity. This protocol effectively complements previous Truce-Smiles rearrangement methods involving -sulfonyl acrylamides.
View Article and Find Full Text PDFOrg Biomol Chem
December 2024
School of Pharmaceutical and Chemical Engineering & Institute for Advanced Studies, Taizhou University, 1139 Shifu Avenue, Taizhou 318000, Zhejiang, China.
An efficient synthesis of sulfonate esters through reductive addition of sodium sulfinates to pillar[4]arene[1]quinone has been established (15 examples). Compared to the arylsulfonylation of -quinone with sodium arylsulfinates under other acidic conditions, this work affords the hydroquinone-type 4--sulfonyl derivatives by using glyoxylic acid monohydrate as a promoter. The protocol features mild reaction conditions and high selectivity and is an alternative protocol for the -sulfonylation of pillar[4]arene[1]hydroquinone.
View Article and Find Full Text PDFJ Org Chem
December 2024
School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, China.
A gold-catalyzed sulfonylation of aryl/vinyl iodides to synthesize aryl sulfones facilitated by the ligand-enabled Au(I)/Au(III) redox catalysis was developed. In the reaction, aryl sodium sulfinates or sulphinic acids can react smoothly with aryl/vinyl iodides to directly construct various aryl sulfones. The strong synthetic capabilities of sulfone synthesis are demonstrated by its easily available and handled reagents, good functional group compatibility, and late-stage application of complicated biomolecules.
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