Sulfonium-Claisen rearrangement leveraged by the gold-catalyzed formation of allyl sulfonium intermediates has enabled an exceptional level of regio- and enantiocontrol for the synthesis of skipped 1,4-dienes. However, the application of cinnamyl thioether derivatives to the sulfonium-Claisen rearrangement has been unsuccessful so far due to the extensive dissociation of the cinnamyl cation. By fine-tuning bisphosphine ligands, we were able to engage cinnamyl thioethers in the [3,3]-sigmatropic rearrangement, delivering the desired 1,4-dienes in a highly enantioselective manner and in good yields. The resulting products could be transformed into optically active 2-chromanones and 4-chromenes having a vinyl moiety.
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-Cyanomethylation of aryl fluoroalkyl sulfoxides a sulfonium-Claisen rearrangement.
Org Biomol Chem
February 2024
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua 321004, China.
We hereby report the -cyanomethylation of aryl fluoroalkyl sulfoxides with acetonitrile through a sulfonium-Claisen-type rearrangement. This reaction enables the incorporation of two valuable functional groups, such as the cyanomethyl group and the fluoroalkylthio group, into arenes. Remarkably, fluoroalkylthio groups, such as SCFH and SCFH, bearing active hydrogen, are well tolerated by the reaction.
View Article and Find Full Text PDFEnantioselective Sulfonium-Claisen Rearrangement with Cinnamyl Thioethers.
Org Lett
June 2023
Department of Chemistry, Research Institute for Natural Sciences and Center for New Directions in Organic Synthesis (CNOS), Hanyang University, 222 Wangsimni-ro, Seongdong-gu, Seoul 04763, Korea.
Sulfonium-Claisen rearrangement leveraged by the gold-catalyzed formation of allyl sulfonium intermediates has enabled an exceptional level of regio- and enantiocontrol for the synthesis of skipped 1,4-dienes. However, the application of cinnamyl thioether derivatives to the sulfonium-Claisen rearrangement has been unsuccessful so far due to the extensive dissociation of the cinnamyl cation. By fine-tuning bisphosphine ligands, we were able to engage cinnamyl thioethers in the [3,3]-sigmatropic rearrangement, delivering the desired 1,4-dienes in a highly enantioselective manner and in good yields.
View Article and Find Full Text PDFRevisiting Aromatic Claisen Rearrangement Using Unstable Aryl Sulfonium/Iodonium Species: The Strategy of Breaking Up the Whole into Parts.
Acc Chem Res
August 2022
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, 688 Yingbin Road, Jinhua321004, China.
Since Ludwig Claisen's discovery of the sigmatropic rearrangement of allyl aryl ethers in 1912, aromatic Claisen rearrangement has continuously attracted the attention of both experimental and theoretical chemists. Over more than a century of growth, this protocol has proven to be a practical and powerful synthetic tool in many aspects. However, the reaction scope has long been limited to aryl ethers and their or analogs until the serendipitous discovery of aromatic iodonium-Claisen rearrangement by Oh et al.
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