An unexpected regioselective synthesis of vinyl triflones was developed. This iodine-mediated C-H triflylation of styrenes with CF3SO2Na occurred at room temperature affording various vinyl triflones, which could be used for the preparation of other CF3SO2-containing compounds.
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http://dx.doi.org/10.1039/c6ob01567k | DOI Listing |
J Org Chem
June 2024
Key Laboratory of Biocatalysis & Chiral Drug Synthesis of Guizhou Province, Generic Drug Research Center of Guizhou Province, School of Pharmacy, Zunyi Medical University, Zunyi 563000, China.
Here, we present a straightforward α--selective hydroboration of alkynyl sulfones with NHC-boranes without the need for a catalyst. This reaction is compatible with a wide range of substrates for efficiently producing structurally diverse α-borylated vinyl sulfones in satisfactory yields. The hydride transfer from NHC-borane to alkynyl triflone is studied by density functional theory (DFT) calculations for -hydroboration.
View Article and Find Full Text PDFJ Org Chem
April 2023
Key Laboratory of Biocatalysis & Chiral Drug Synthesis of Guizhou Province, Generic Drug Research Center of Guizhou Province, School of Pharmacy, Zunyi Medical University, Zunyi 563000, China.
A visible-light-initiated trifluoromethylation/remote aliphatic C-H alkynylation of α-alkyl-substituted vinyl azides using acetylenic triflones as both the trifluoromethyl and alkyne donors is described. The reaction occurred under environmentally benign and radical initiator-free reaction conditions, affording γ-alkynylated trifluoromethyl ketone derivatives with a broad scope of substituents. Mechanistic studies suggested that the reaction is initiated a triplet-triplet energy transfer between the 4CzIPN catalyst and acetylenic triflone, followed by fragmentation to generate a trifluoromethyl radical and an alkynyl radical.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
April 2023
Laboratory of Organic Chemistry, ETH Zürich, Vladimir-Prelog-Weg 3, 8093, Zürich, Switzerland.
Trifluoromethylsulfones (triflones) are useful compounds for synthesis and beyond. Yet, methods to access chiral triflones are scarce. Here, we present a mild and efficient organocatalytic method for the stereoselective synthesis of chiral triflones using α-aryl vinyl triflones, building blocks previously unexplored in asymmetric synthesis.
View Article and Find Full Text PDFWith an ever-growing emphasis on sustainable synthesis, aerobic C-H activation (the use of oxygen in air to activate C-H bonds) represents a highly attractive conduit for the development of novel synthetic methodologies. Herein, we report the air mediated functionalisation of various saturated heterocycles and ethers aerobically generated radical intermediates to form new C-C bonds using acetylenic and vinyl triflones as radical acceptors. This enables access to a variety of acetylenic and vinyl substituted saturated heterocycles that are rich in synthetic value.
View Article and Find Full Text PDFChemistry
June 2018
CAI Difracción de Rayos X, Facultad de Química, Universidad Complutense de Madrid, Spain.
Functionalized ynones can be activated by Tf C=CH , which was generated in situ, to form zwitterionic species. These species were trapped in an intramolecular fashion by several nucleophiles to generate two major types of triflones in a divergent manner. Through fine-tuning of the reaction temperature, bis(triflyl)-6-membered- or (triflyl)-5-membered-fused-heterocycles were achieved in reasonable yields in a totally selective manner.
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