Due to the strong electron-withdrawing nature and high lipophilicity of trifluoromethoxy group (OCF ), methods for introducing OCF into organic molecules are in high demand. However, the research area of direct enantioselective trifluoromethoxylation is still in the embryonic stage, with limited enantioselectivity and/or reaction types. Here, we describe the first copper-catalyzed enantioselective trifluoromethoxylation of propargyl sulfonates using trifluoromethyl arylsulfonate (TFMS) as the trifluoromethoxy source in up to 96 % ee.
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Copper-Catalyzed Enantioselective Trifluoromethoxylation of Propargyl Sulfonates.
Angew Chem Int Ed Engl
April 2023
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, China.
Due to the strong electron-withdrawing nature and high lipophilicity of trifluoromethoxy group (OCF ), methods for introducing OCF into organic molecules are in high demand. However, the research area of direct enantioselective trifluoromethoxylation is still in the embryonic stage, with limited enantioselectivity and/or reaction types. Here, we describe the first copper-catalyzed enantioselective trifluoromethoxylation of propargyl sulfonates using trifluoromethyl arylsulfonate (TFMS) as the trifluoromethoxy source in up to 96 % ee.
View Article and Find Full Text PDFPalladium(II)-Catalyzed Enantioselective Aminotrifluoromethoxylation of Unactivated Alkenes using CsOCF as a Trifluoromethoxide Source.
Angew Chem Int Ed Engl
February 2019
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
Asymmetric Pd -catalyzed intramolecular aminotrifluoromethoxylation of unactivated alkenes using readily accessible and stable CsOCF as a trifluoromethoxide source has been developed, which affords a wide variety of enantiomerically enriched β-substituted OCF -containing piperidines in good yields. Introducing a sterically bulky group into pyridine-oxazoline (Pyox) ligands is crucial to increasing both reactivity and enantioselectivity for the reaction. Additionally, the reaction features good functional group compatibility and mild reaction conditions.
View Article and Find Full Text PDFEnantioselective Construction of Trifluoromethoxylated Stereogenic Centers by a Nickel-Catalyzed Asymmetric Suzuki-Miyaura Coupling of Secondary Benzyl Bromides.
Angew Chem Int Ed Engl
September 2017
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
Trifluoromethoxy-substituted stereogenic centers can be constructed with high enantioselectivity by a nickel-catalyzed Suzuki-Miyaura coupling of readily available α-bromobenzyl trifluoromethyl ethers with a variety of aryl pinacol boronates. The coupling proceeds under mild reaction conditions, and a variety of common functional groups, such as fluoride, chloride, bromide, ester, enolizable ketone, nitro, cyano, amino, and vinyl moieties, were well tolerated. Furthermore, the reaction can be easily scaled up to gram quantities without a decrease in enantioselectivity.
View Article and Find Full Text PDFAsymmetric silver-catalysed intermolecular bromotrifluoromethoxylation of alkenes with a new trifluoromethoxylation reagent.
Nat Chem
June 2017
State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China.
Fluorinated organic compounds are becoming increasingly important in pharmaceuticals, agrochemicals and materials science. The introduction of trifluoromethoxy groups into new drugs and agrochemicals has attracted much attention due to their strongly electron-withdrawing nature and high lipophilicity. However, synthesis of trifluoromethoxylated organic molecules is difficult owing to the decomposition of trifluoromethoxide anion and β-fluoride elimination from transition-metal-trifluoromethoxide complexes, and no catalytic enantioselective trifluoromethoxylation reaction has been reported until now.
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