Base-Catalyzed Intramolecular Defluorination/O-Arylation Reaction for the Synthesis of 3-Fluoro-1,4-oxathiine 4,4-Dioxide

Lei Kang; Jinlong Zhang; Huameng Yang; Jinlong Qian; Gaoxi Jiang

doi:10.1055/a-1387-8862

Synlett, Table of Contents

Synlett 2021; 32(08): 785-789
DOI: 10.1055/a-1387-8862

letter

Base-Catalyzed Intramolecular Defluorination/O-Arylation Reaction for the Synthesis of 3-Fluoro-1,4-oxathiine 4,4-Dioxide

Authors

Lei Kang

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Excellence in Molecular Synthesis, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. of China

^bUniversity of Chinese Academy of Sciences, Beijing 100049, P. R. of China
Jinlong Zhang

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Excellence in Molecular Synthesis, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. of China
Huameng Yang

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Excellence in Molecular Synthesis, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. of China
Jinlong Qian∗

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Excellence in Molecular Synthesis, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. of China
Gaoxi Jiang∗

^aState Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Excellence in Molecular Synthesis, Suzhou Research Institute, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. of China

Abstract

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Abstract

A novel process involving base-catalyzed intramolecular defluorination/O-arylation of readily available α-fluoro-β-one-sulfones was realized and provided a series of 3-fluoro-1,4-oxathiine 4,4-dioxide derivatives in good to excellent yields. Unlike traditional defluorination reactions with stoichiometric base as the deacid reagent, this process is triggered by a catalytic amount of base (TMG: tetramethylguanidine) and molecular sieves serve as both an adsorbent to remove HF acid and an activator to assist C–F bond cleavage.

Key words

base catalysis - defluorination - O-arylation - metal-free reactions - 1,4-oxathiines

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References

References and Notes
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13 3-Fluoro-2-phenylbenzo[b][1,4]oxathiine 4,4-dioxide (2a); Typical Procedure Substrate 1a (0.2 mmol, 1.0 equiv), tetramethylguanidine (TMG, 0.01 mmol, 100 μL of 0.1 M TMG in DMF), and 3 Å molecular sieves (100 mg, 3 Å molecular sieves were activated at 180 °C for 5 h) were mixed in anhydrous DMF (1.0 mL) at 80 °C for 10 h. After the reaction was complete, the solvent was evaporated and the crude mixture was purified by flash chromatography on silica gel (PE/EtOAc/DCM = 12:1:1) to afford the desired compound 2a in 90% yield; white solid; mp 131–133 °C. ¹H NMR (400 MHz, chloroform-d): δ = 8.04–7.97 (m, 1 H), 7.80 (dd, J = 6.7, 2.9 Hz, 2 H), 7.72–7.64 (m, 1 H), 7.53 (dd, J = 5.0, 1.9 Hz, 3 H), 7.48–7.38 (m, 2 H). ¹³C NMR (100 MHz, chloroform-d): δ = 150.0, 144.4 (d, J = 21.1 Hz), 141.6 (d, J = 276.7 Hz), 134.2, 131.6, 128.9, 128.0, 127.9, 126.2 (d, J = 6.2 Hz), 125.6, 123.2 (d, J = 2.6 Hz), 119.2. ¹⁹F NMR (376 MHz, chloroform-d): δ = –175.89. HRMS (ESI): m/z calcd for C₁₄H₉FNaO₃S [M + Na]⁺: 299.0149; found: 299.0145.

Supplementary Material

Supporting Information (PDF)