Oxy-Cope rearrangements of fluorinated divinylcyclohexanols: a modular method for the construction of selectively fluorinated cyclic ketones

Abstract

Oxy-Cope rearrangements of fluorinated divinylcyclohexanols afford access to cyclodecenones containing from two to five fluorine atoms.

References

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12. Selected data for 9c: colourless rhombi, mp 94 °C; (Found: C, 59.68; H, 6.61. Calc. for C₁₃H₁₇F₃O₂: C, 59.54; H, 6.49%); δ_H(300 MHz, CDCl₃) 5.32 (dddd, ³J 32.4, J 11.4, J 6.3, J 3.0, 1H), 4.16 (dd, ²J 11.4, J 5.5, 1H), 3.72 (t, J 3.4, 1H), 3.48 (ddt, ²J 11.4, J 13.0, J 3.1, 1H), 3.10 (dd, J 19.1, J 10.5, 1H), 2.88 (dddd, ³J 31.6, J 10.8, ³J 5.5, J 2.9, 1H), 2.38–2.30 (m, 2H), 2.19–2.05 (m, 3H), 2.04–1.95 (m, 1H), 1.86 (dtd, J 16.8, 10.9, 5.5, 1H), 1.73 (ddt, J 19.8, ²J 14.3, J 5.5, 1H), 1.63–1.55 (m, 1H), 1.40 (d, ²J 14.3, 1H), 1.31 (q, J 14.0, 1H); δ_F(282 MHz, CDCl₃)–101.9 (dd, ²J 255.6, ³J 26.7, 1F), –109.5 (dd, ²J 255.6, ³J 31.7, 1F), –124.8 (t, ³J 31.2, 1F); ¹³δ_C(75 MHz, CDCl₃) 207.5, 150.5 (ddd, ²J 260.5, ²J 38.4, ²J 27.7), 117.6 (ddd, ¹J 244.7, ¹J 252.1, ²J 37.9), 113.0, 83.2, 69.5, 40.9 (dd, ²J 27.1, ²J 21.5), 38.5, 29.1, 28.5, 23.1, 22.0, 20.5; ν_max/cm^–1 1711.9; m/z(CI) 280 (M+NH₄⁺).
13. J. Stonehouse, P. Adell, J. Keeler and A. J. Shaka, J. Am. Chem. Soc., 1994, 116, 6037.
14. Crystal data for 9a: C₁₃H₁₇ClF₂O₂, M= 278.7, triclinic, a= 8.0670(2), b= 8.3194(3), c= 10.5779(3)Å, U= 633.65(3)ų, T= 150(2) K, space group P1̄, Z= 2, µ(Mo-K_α) 0.318 mm^–1, 10852 reflections measured, 2555 unique (R_int= 0.0441) which were used in all calculations. The final wR(F²) was 0.0718 (all data). CCDC 182/1482. See http://www.rsc.org/suppdata/cc/1999/2535/ for crystallographic data in .cif format.