Y. Itoh, K. Mikami / Journal of Fluorine Chemistry 127 (2006) 539–544
543
20 min at the temperature. Next, iPr2NH (44.9 ml, 0.32 mmol)
was added to the solution and stirred for another 20 min. Then,
the reaction mixture was cooled to À78 8C. To the mixture was
added gaseous CF3I (ca. 200 mg, ca. 1.0 mmol) with a cannula
followed by Et3B (0.2 ml of 1.0 M solution in hexane,
0.2 mmol). The reaction mixture was stirred for 2 h at
À78 8C and then quenched by acetic acid (0.12 ml of 5 M
solution in THF) at the temperature. After warming to room
temperature, BTF (10 ml, 0.082 mmol) was added as an internal
standard. The yield was determined by 19F NMR analysis of the
crude mixture (74%) (2a).
J = 10.2 Hz). IR (neat): 3068, 3032, 2922, 1734, 1605, 1497,
1456, 1419, 1377, 1261, 1154, 1096, 750, 700 cmÀ1. EI-MS m/
z: 216 [M+ꢀ].
3.9. 7-Trifluoromethyl-6-undecanone (2f)
1H NMR (CDCl3): d 0.90 (t, J = 3.9 Hz, 6H), 1.18–1.41 (m,
8H), 1.53–1.65 (m, 2H), 1.65–1.79 (m, 1H), 1.81–1.97 (m, 1H),
2.47 (dt, J = 18.0, 7.2 Hz, 1H), 2.61 (dt, J = 7.4, 18.0 Hz, 1H),
3.11–3.26 (m, 1H). 13C NMR (CDCl3): d 13.6, 13.8, 22.4, 22.7,
25.59, 25.62, 29.0, 31.1, 43.6, 55.6 (q, J = 24.4 Hz), 124.9 (q,
J = 280.7 Hz), 204.5. 19F NMR (CDCl3): d 67.4 (d, J = 9.0 Hz).
IR (neat): 2966, 2938, 2870, 1731, 1263, 1164 cmÀ1. EI-MS m/
z: 238 [M+ꢀ].
3.4. 2-Trifluoromethyl-cyclohexanone (2a)
1H NMR (CDCl3): d 1.62–1.88 (m, 3H), 1.92–2.14 (m, 2H),
2.24–2.39 (m, 2H), 2.42–2.53 (m, 1H), 2.98–3.13 (m, 1H). 13
C
3.10. 2-Methyl-2-trifluoromethyl-cyclohexanone (2j)
NMR (CDCl3): d 23.7, 27.1, 27.5 (q, J = 2.4 Hz), 42.2, 53.6(q,
J = 25.7 Hz), 124.6(q, J = 279.5 Hz), 203.0. 19F NMR
(CDCl3): d À69.3(d, 7.9 Hz). IR (neat): 2954, 2876, 2364,
1729, 1272, 1170, 1125, 1060 cmÀ1. EI-MS m/z: 166 [M+ꢀ]
1H NMR (CDCl3): d 1.36 (s, 3H), 1.70–2.00 (m, 5H), 2.06–
2.20 (m, 1H), 2.35–2.58 (m, 2H). 13C NMR (CDCl3): d 17.7 (q,
J = 2.4 Hz), 20.5, 26.4, 33.5, 39.4, 53.7 (q, J = 23.2 Hz), 126.5
(q, J = 283.2 Hz), 206.2. 19F NMR (CDCl3): d À73.6 (s). IR
(neat): 2936, 2874, 1725, 1274, 1170, 1137 cmÀ1. EI-MS m/z:
180 [M+ꢀ].
3.5. 1,1,1-Trifluoro-4,4-dimethyl-5-phenyl-3-pentanone
(2b)
1H NMR (CDCl3): d 1.16 (s, 6H), 2.81 (s, 2H), 3.17 (q,
J = 9.9 Hz, 2H), 7.07 (ddd, J = 1.7, 2.1, 6.3 Hz, 2H), 7.19–7.32
(m, 3H). 13C NMR (CDCl3): d 23.8, 41.4 (q, J = 28.1 Hz), 45.3,
48.9, 123.9 (q, J = 277.1 Hz), 126.8, 128.2, 130.2, 136.8, 205.2.
19F NMR (CDCl3): d À63.0 (t, J = 9.8 Hz). IR (neat): 3034,
2976, 1721, 1369, 1282, 1133, 1100 cmÀ1. EI-MS m/z: 244
[M+ꢀ].
3.11. 2-Phenyl-2-trifluoromethyl-cyclohexanone (2k)
1H NMR (CDCl3): d 1.63–1.86 (m, 3H), 1.89–2.00 (m, 1H),
2.12–2.25 (m, 1H), 2.31–2.40 (m, 2H), 2.91 (qd, J = 3.0,
14.4 Hz, 1H), 7.29–7.35 (m, 2H), 7.35–7.47 (m, 3H). 13C NMR
(CDCl3): d 20.2, 27.4, 29.9 (q, J = 2.4 Hz), 39.8, 62.2 (q,
J = 22.0 Hz), 125.1 (q, J = 283.2 Hz), 128.7, 128.8, 129.0,
131.8, 204.7. 19F NMR (CDCl3): d À72.9 (s). IR (neat): 3066,
2954, 2874, 1725, 1282, 1255, 1176, 1152 cmÀ1. EI-MS m/z:
242 [M+ꢀ].
3.6. 2-Trifluoromethyl-cyclopentanone (2c)
1H NMR (CDCl3): d 1.77–2.00 (m, 1H), 2.01–2.21 (m, 2H),
2.22–2.48 (m, 3H), 2.78–2.97 (qm, J = 9.6 Hz, 1H). 13C NMR
(CDCl3): d 20.0, 24.4, 38.5, 51.1 (q, J = 26.9 Hz), 124.6 (q,
J = 278.3 Hz), 209.4. 19F NMR (CDCl3): d À67.9 (d, J = 10.5).
IR (neat): 2986, 2896, 2366, 2344, 1758, 1638, 1367, 1313,
1257, 1187, 1151, 1096, 1046 cmÀ1. EI-MS m/z: 152 [M+ꢀ].
References
[1] (a) J.-A. Ma, D. Cahard, Chem. Rev. 104 (2004) 6119–6146;
(b) K. Mikami, Y. Itoh, M. Yamanaka, Chem. Rev. 104 (2004) 1–16;
(c) T. Hiyama, K. Kanie, T. Kusumoto, Y. Morizawa, M. Shimizu,
Organofluorine Compounds, Springer-Verlag, Berlin Heidelberg, 2000;
(d) V.A. Soloshonok (Ed.), Enantiocontrolled Synthesis of Fluoro-
Organic Compounds, Wiley, Chichester, 1999;
3.7. 2-Trifluoromethyl-cycloheptanone (2d)
(e) P.V. Ramachandran (Ed.), Asymmetric Fluoroorganic Chemistry,
Synthesis, Applications, and Future Directions, American Chemical
Society, 2000;
1H NMR (CDCl3): d 1.22–1.48 (m, 2H), 1.48–1.75 (m, 2H),
1.86–2.05 (m, 3H), 2.09–2.20 (m, 1H), 2.54–2.61 (m, 2H),
3.16–3.31 (qdd, J = 4.1, 8.9, 11.1 Hz, 1H). 13C NMR (CDCl3):
d 24.4, 24.7 (q, J = 2.4 Hz), 27.5, 29.1, 43.1, 55.5 (q,
J = 24.5 Hz), 124.9 (q, J = 280.8 Hz), 205.9. 19F NMR
(CDCl3): d À69.0 (d, J = 9.0 Hz). IR (neat): 2940, 2866,
1721, 1178, 1151, 1096 cmÀ1. EI-MS m/z: 180 [M+ꢀ].
(f) R.D. Chambers (Ed.), Organofluorine Chemistry, Springer, Berlin,
1997;
(g) K. Iseki, Tetrahedron 54 (1998) 13887–13914;
(h) I. Ojima, J.R. McCarthy, J.T. Welch (Eds.), Biomedical Frontiers of
Fluorine Chemistry, American Chemical Society, Washington DC, 1996;
(i) B. E. Smart (Ed.), Chem. Rev. 96 (1996) 1555–1824 (Thematic issue
of fluorine chemistry).
(j) R.E. Banks, B.E. Smart, J.C. Tatlow (Eds.), Organofluorine Chemistry:
Principles and Commercial Applications, Plenum Press, New York, 1994;
(k) M.A. McClinton, D.A. McClinton, Tetrahedron 48 (1992) 6555–
6666;
3.8. 1,1,1-Trifluoro-5-phenyl-3-pentanone (2e)
1H NMR (CDCl3): d 2.80–3.00 (m, 4H), 3.19 (q,
J = 10.2 Hz, 2H), 7.14–7.35 (m, 5H). 13C NMR (CDCl3): d
29.2, 44.9, 46.5 (q, J = 28.1 Hz), 123.5 (q, J = 277.1 Hz), 126.4,
128.3, 128.6, 140.1, 199.1. 19F NMR (CDCl3): d -62.9 (t,
(l) M. Hudlicky, Chemistry of Organic Fluorine Compounds, 2nd ed.,
Ellis Horwood, Chichester, 1976.
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