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Synlett 2012; 23(7): 1064-1068
DOI: 10.1055/s-0031-1290757
DOI: 10.1055/s-0031-1290757
letter
Meerwein’s Reagent Mediated, Significantly Enhanced Nucleophilic Fluorination on Alkoxysilanes
Weitere Informationen
Publikationsverlauf
Received: 24. Januar 2012
Accepted after revision: 14. Februar 2012
Publikationsdatum:
05. April 2012 (online)
Abstract
We developed a new facile method to fluorosilanes from alkoxysilanes using Meerwein’s reagent. Our protocol afforded fluorosilanes in excellent yields in various organic solvents including acetonitrile under mild reaction conditions at room temperature. We also proposed a reaction mechanism with the probable silyloxonium intermediates.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
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References and Notes
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- 30 Typical Procedure for the Synthesis of Fluorosilanes: A dry and nitrogen-flushed 10 mL screw-capped vial was charged with alkoxysilane (1, 1.0 mmol), MeCN (5.0 mL) followed by the addition of Me3OBF4 (147.9 mg, 1.0 mmol) or Et3OBF4 (189.9 mg, 1.0 mmol). The reaction mixture was stirred at 50 °C for 30 min and quenched by dropwise addition of H2O. It was then diluted with CH2Cl2; the organic layer was washed with brine, dried over anhyd MgSO4, and evaporated under reduced pressure. The crude mixture was purified by chromatography on silica gel (5% EtOAc–hexane as eluent) to give the corresponding fluorosilane as a colorless liquid.(4-Bromophenyl)di(prop-2-enyl)fluorosilane (2a): colorless liquid. 1H NMR (270 MHz, CDCl3): δ = 1.96–2.01 (m, 4 H), 4.97–5.06 (m, 4 H), 5.70–5.86 (m, 2 H), 7.44 (d, J = 8.1 Hz, 2 H), 7.56 (d, J = 8.1 Hz, 2 H). 13C NMR (68 MHz, CDCl3): δ = 21.0, 21.2, 116.3, 125.6, 130.8, 130.85, 131.2, 135.06, 135.09. 19F NMR (376 MHz, CDCl3): δ = –171.93. HRMS (FAB+): m/z [M – H]+ calcd for C12H13BrFSi: 282.9954; found: 282.9935.Fluoro[phenyldi(prop-2-enyl)]silane (2b): colorless liquid. 1H NMR (270 MHz, CDCl3): δ = 1.98–2.04 (m, 4 H), 4.97–5.06 (m, 2 H), 5.74–5.89 (m, 2 H), 7.38–7.50 (m, 3 H), 7.58–7.62 (m, 2 H). 13C NMR (68 MHz, CDCl3): δ = 21.1, 21.3, 115.9, 128.0, 130.6, 131.3, 133.5, 133.6. 19F NMR (470 MHz, CDCl3): δ = –172.82. HRMS (FAB+): m/z [M – H]+ calcd for C12H15FSi: 206.0927; found: 206.0921.Fluoro[diphenyl(prop-2-enyl)]silane (5): colorless liquid. 1H NMR (400 MHz, CDCl3): δ = 2.22–2.25 (m, 2 H), 4.95–5.04 (m, 2 H), 5.79–5.86 (m, 1 H), 7.38–7.47 (m, 6 H), 7.61–7.63 (m, 4 H). 13C NMR (100 MHz, CDCl3): δ = 21.7, 21.8, 116.2, 128.0, 130.7, 131.2, 132.7, 132.8, 134.25, 134.27. 19F NMR (376 MHz, CDCl3): δ = –170.8. HRMS (EI+): m/z [M]+ calcd for C15H15FSi: 242.0927; found: 242.0927.Fluorotri(prop-2-enyl)silane (7): colorless liquid. 1H NMR (400 MHz, CDCl3): δ = 1.76–1.79 (m, 6 H), 4.97–5.02 (m, 6 H), 5.75–5.82 (m, 3 H). 13C NMR (100 MHz, CDCl3): δ = 20.5, 20.7, 115.6, 131.4. 19F NMR (376 MHz, CDCl3): δ = –170.2. CAS registry no. 429-89-0
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