Synlett 2015; 26(01): 63-66
DOI: 10.1055/s-0034-1379599
cluster
© Georg Thieme Verlag Stuttgart · New York

Highly Controlled Ring-Opening of Siloxydifluorocyclopropanes: A Versatile Route to Cyclic Fluoroketones

Yoshiya Kageshima
Division of Molecular Science, Graduate School of Science and Technology, Gunma University, Kiryu, Gunma 376-8515, Japan   Fax: +81(277)301280   Email: amii@gunma-u.ac.jp
,
Chiharu Suzuki
Division of Molecular Science, Graduate School of Science and Technology, Gunma University, Kiryu, Gunma 376-8515, Japan   Fax: +81(277)301280   Email: amii@gunma-u.ac.jp
,
Kojun Oshiro
Division of Molecular Science, Graduate School of Science and Technology, Gunma University, Kiryu, Gunma 376-8515, Japan   Fax: +81(277)301280   Email: amii@gunma-u.ac.jp
,
Hideki Amii*
Division of Molecular Science, Graduate School of Science and Technology, Gunma University, Kiryu, Gunma 376-8515, Japan   Fax: +81(277)301280   Email: amii@gunma-u.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 22 October 2014

Accepted after revision: 31 October 2014

Publication Date:
20 November 2014 (online)


Abstract

A convenient access to cyclic fluoroketones that involves base-promoted ring-opening of siloxydifluorocyclopropanes is presented. Selective formation of gem-difluorinated cycloalkanones and monofluorinated enones has been achieved.

Supporting Information

 
  • References and Notes

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  • 18 Formation of Siloxydifluorocyclopropanes 2; General Procedure: To a solution of silyl enol ether 1a (851 mg, 5.0 mmol) in diglyme (20 mL), was added a diglyme solution (20 mL) of sodium bromodifluoroacetate (1.48 g, 7.5 mmol) at 150 °C. The reaction mixture was stirred for 10 min at 150 °C, then, after cooling to room temperature, the reaction was quenched by the addition of water. Organic materials were extracted three times with hexane and the combined organic layers were washed with brine and dried over Na2SO4. After removal of the solvent under reduced pressure, the residue was purified by silica gel column chromatography (hexane–EtOAc, 50:1) to give 2a 15,16 (800 mg, 73%) as a colorless oil. 1H NMR (400 MHz, CDCl3, TMS): δ = 2.22–2.10 (m, 1 H), 1.96–1.78 (m, 2 H), 1.64–1.40 (m, 2 H), 1.38–1.20 (m, 4 H), 0.17 (s, 9 H). 19F NMR (376 MHz, CDCl3, C6F6): δ = 25.9 (dd, J F–F = 161.7, J H–F = 23.3 Hz, 1 F), 15.4 (d, J F–F = 161.7 Hz, 1 F). GC-MS: m/z (%) = 220 (4) [M]+, 205 (10), 81 (31), 73 (100).
  • 19 Formation of gem-Difluorinated Cycloalkanones 3; General Procedure: A mixture containing siloxydifluorocyclopropane 2a (594 mg, 2.7 mmol) and Na2CO3 (286 mg, 2.7 mmol) in MeOH (30 mL) was stirred at room temperature under an atmosphere of argon for 30 min. Organic materials were extracted three times with Et2O, and the combined organic layers were washed with brine and dried over Na2SO4. After removal of the solvent under reduced pressure, the residue was purified by silica gel column chromatography (hexane–EtOAc, 5:1) to give 3a (283 mg, 71%) as a colorless oil. 1H NMR (400 MHz, CDCl3, TMS): δ = 2.70–2.64 (m, 2 H), 2.15–2.03 (m, 2 H), 1.88–1.80 (m, 2 H), 1.76–1.68 (m, 2 H), 1.67–1.60 (m, 2 H). 19F NMR (376 MHz, CDCl3, C6F6): δ = 56.9 (s, 2 F). 13C NMR (75 MHz, CDCl3): δ = 201.3 (t, J = 24.9 Hz), 118.6 (t, J = 249.2 Hz), 38.8, 33.7 (t, J = 23.7 Hz), 27.5, 23.6, 22.8 (t, J = 5.7 Hz). GC-MS: m/z (%) = 148 (3) [M]+, 119 (15), 84 (61), 55 (100). IR (NaCl): 1739 cm–1. Anal. Calcd for C7H10F2O: C, 56.75; H, 6.80. Found: C, 56.41; H, 6.89.
  • 20 Formation of Fluorinated Cyclic Enones 4; General Procedure: To a solution of siloxydifluorocyclopropane 2a (66.0 mg, 0.3 mmol) in diglyme (3.0 mL) was added TBAF (1 M in THF, 0.3 mL, 0.3 mmol) at –78 °C under an atmosphere of argon. The reaction mixture was then stirred for 150 min at room temperature. Organic materials were extracted three times with Et2O and the combined organic layers were washed with brine and dried over Na2SO4. After removal of the solvent under reduced pressure, the residue was purified by silica gel column chromatography (hexane–EtOAc, 5:1) to give 4a 21 (34.9 mg, 91%) as a colorless oil. 1H NMR (300 MHz, CDCl3, TMS): δ = 6.25 (dt, J H–F = 21.6, 6.6 Hz, 1 H), 2.70–2.64 (m, 2 H), 1.89–1.87 (m, 2 H), 1.74–1.62 (m, 4 H). 19F NMR (282 MHz, CDCl3, C6F6): δ = 43.0 (d, J H–F = 21.6 Hz, 1 F). GC-MS: m/z (%) = 128 (4) [M]+, 85 (64), 72 (100). IR (NaCl): 1698 cm–1.
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