G. Blay et al. / Tetrahedron 58 (2002) 8565–8571
8569
3.3.5. 3,3,3-Trifluoro-2-hydroxy-2-(2-naphthyl)propa-
noic acid (4e). From 1 g (3.36 mmol) of 3e was obtained
900 mg (99%) of 4e: mp 164–1668C (EtOH); IR (KBr) n
(4j). From 1 g (3.20 mmol) of 3j was obtained 892 mg
(98%) of 4j: mp 80–828C (EtOH), IR (KBr) n 3509,
1741 cm21
;
1H NMR (d, CDCl3) 2.02 (1H, td, J¼9.0,
3410, 3500–2400, 1740 cm21
;
1H NMR (d, d6-DMSO)
2.6 Hz), 1.90 (1H, td, J¼9.0, 3.3 Hz), 1.54 (1H, m), 1.24
8.22 (1H, s), 8.02–7.89 (3H, m), 7.76 (1H, d, J¼8.7 Hz),
7.60–7.50 (2H, m); 13C NMR (d, d6-DMSO) 169.6 (C),
133.3 (C), 132.6 (C), 132.5 (C), 128.7 (CH), 128.1 (CH),
127.8 (CH), 127.3 (CH), 127.0 (CH), 126.3 (CH), 124.3
(15H, m), 0.86 (3H, t, J¼5.3 Hz); 13C NMR (d, CDCl3)
1
2
173.7 (C), 123.3 (CF3, q, JC–F¼284 Hz), 77.9 (C, q, JC–
¼28 Hz), 31.9 (CH2), 31.5 (CH2), 29.5 (CH2), 29.4 (CH2),
F
29.3 (CH2), 29.2 (CH2), 22.7 (CH2), 22.4 (CH2), 14.1
(CH3); 19F NMR (d, CDCl3) 279.0 (s); MS (CI) m/z 285
(Mþþ1, 0.1), 246 (100), 199 (66); HRMS 285.1674,
C13H24F3O3 required 285.1678.
1
2
(CH, q, JC–F¼284 Hz), 124.0 (CH), 78.3 (C, q, JC–
¼28 Hz); 19F NMR (d, d6-DMSO) 274.6 (s); MS (EI) m/z
F
270 (Mþ, 75), 225 (100), 155 (88), 128 (70); HRMS
270.0514, C13H9F3O3 required 270.0504.
3.3.11. 2-Hydroxy-2-trifluoromethyl-12-tridecenoic acid
(4k). From 1 g (3.09 mmol) of 3a was obtained 890 mg
(98%) of 4k: mp 78–798C (EtOH); IR (KBr) n 3520, 3500–
3.3.6. 2-Hydroxy-3-phenyl-2-trifluoromethylpropanoic
acid (4f). From 1 g (3.82 mmol) of 3f was obtained
875 mg (98%) of 4f: mp 118–1208C (EtOH); IR (KBr) n
1
2800, 1740 cm21; H NMR (d, d6-DMSO) 5.77 (1H, ddq,
3437, 3411, 3400–2800, 1747 cm21
;
1H NMR (d, d6-
J¼6.7, 10.3, 16.5 Hz), 4.96 (1H, br d, J¼16.5 Hz), 4.91 (1H,
br d, J¼10.3 Hz), 1.99 (2H, q, J¼6.8 Hz), 1.84 (1H, td,
J¼12.5, 4.4 Hz), 164 (1H, td, J¼12.5, 4.4 Hz), 1.50–1.10
(14H, m); 13C NMR (d, d6-DMSO) 169.9 (C), 138.9 (CH),
DMSO) 7.27 (5H, br s), 3.20 (1H, d, J¼13.5 Hz), 3.01 (1H,
d, J¼13.5 Hz); 13C NMR (d, d6-DMSO) 169.4 (C), 134.3
(C), 130.8 (CH), 128.2 (CH), 127.2 (CH), 127.8 (CF3, q,
1
1JC–F¼286 Hz), 78.0 (C, q, 2JC–F¼26 Hz), 38.1 (CH2); 19
F
124.5 (CF3, q, JC–F¼280 Hz), 114.6 (CH2), 77.0 (C, q,
NMR (d, d6-DMSO) 276.1 (s); MS (EI) m/z 234 (Mþ, 6),
216 (11), 91 (100); HRMS 234.0510, C10H9F3O3 required
234.0504.
2JC–F¼27 Hz), 33.3 (CH2), 32.3 (CH2), 28.9 (CH2), 28.8
(2 CH2), 28.6 (CH2), 28.3 (CH2), 22.3 (CH2), 13.9 (CH3);
19F NMR (d, d6-DMSO) 276.4 (s); MS (EI) m/z 255
(Mþ2C3H5, 1), 200 (37), 55 (100); HRMS 255.1112,
C11H18F3O3 required 255.1103.
3.3.7. 2-Hydroxy-4-phenyl-2-trifluoromethylbutanoic
acid (4g). From 1 g (3.62 mmol) of 3g was obtained
895 mg (100%) of 4g: mp 105–1068C (EtOH); IR (KBr) n
;
3431, 3500–2800, 1750 cm21 1H NMR (d, d6-DMSO)
7.29 (1H, d, J¼8.1 Hz), 7.26 (1H, d, J¼8.1 Hz), 7.20–7.10
(3H, m), 2.77 (1H, td, J¼12.9, 4.5 Hz), 2.45 (1H, td,
J¼12.9, 4.5 Hz), 2.16 (1H, td, J¼12.9, 4.5 Hz), 1.96 (1H, td,
J¼12.9, 4.5 Hz); 13C NMR (d, d6-DMSO) 169.9 (C), 141.0
(C), 128.8 (CH), 128.6 (CH), 126.4 (CH), 124.8 (CF3, q, JC–
3.3.12. 2-Hydroxy-13-methoxyethoxymethoxy-2-tri-
fluoromethyltridecanoic acid (4l). From 1 g (2.33 mmol)
of 3l was obtained 895 mg (96%) of 4l: mp 42–448C
(EtOH); IR (KBr) n 3396, 1742 cm21; 1H NMR (d, CDCl3)
4.69 (2H, s), 3.68 (1H, dd, J¼6.6, 3.9 Hz), 3.58 (1H, dd,
J¼6.6, 3.9 Hz), 3.53 (2H, t, J¼6.6 Hz), 3.38 (3H, s), 1.96
(1H, td, J¼12.6, 3.8 Hz), 1.80 (1H, td, J¼12.6, 3.8 Hz),
1.62–1.00 (18H, m); 13C NMR (d, CDCl3) 171.4 (C), 123.6
¼285 Hz), 77.1 (C, q, JC–F¼27 Hz), 34.7 (CH2), 28.9
F
1
2
(CH2); 19F NMR (d, d6-DMSO) 276.3; MS (EI) m/z 248
(Mþ, 26), 202 (3), 144 (14), 105 (100), 91 (82); HRMS
248.0659, C11H11F3O3 required 248.0660.
(CF3, q, JC–F¼285 Hz), 95.1 (CH2), 77.5 (C, q, JC–
¼29 Hz), 71.6 (CH2), 68.2 (CH2), 66.5 (CH2), 58.7 (CH3),
F
31.4 (CH2), 29.4 (CH2), 29.3 (CH2), 29.2 (CH2), 29.1 (CH2),
29.0 (CH2), 25.9 (CH2), 22.3 (CH2); 19F NMR (d, CDCl3)
279.2 (s); MS (EI) m/z 401 (Mþþ1, 1), 343 (19), 313 (44),
251 (67), 59 (100); HRMS 401.2146, C18H32F3O6 required
401.2151.
3.3.8. 2-Hydroxy-4-phenyl-2-trifluoromethyl-3-butynoic
acid (4h). From 950 mg (3.49 mmol) of 3h was obtained
827 mg (97%) of 4h: mp 96–988C (EtOH); IR (KBr) n
1
3406, 3073, 2244, 1759 cm21; H NMR (d, CDCl3) 7.49
(2H, dd, J¼8.1, 1.5 Hz), 7.42–7.24 (3H, m), 5.57 (1H, br s,
3.3.13. 2,13-Dihydroxy-2-trifluoromethyltridecanoic
acid (4m). From 200 mg (0.58 mmol) of 3m was obtained
182 mg (99%) of 4m: mp 74–768C (EtOH); IR (KBr) n
OH); 13C NMR (d, CDCl3) 168.6 (C), 132.2 (CH), 129.8
1
(CH), 128.4 (CH), 121.6 (CF3, q, JC–F¼285 Hz), 120.3
(C), 87.9 (C), 79.0 (C), 71.6 (C, q, 2JC–F¼33 Hz); 19F NMR
(d, CDCl3) 278.6 (s); MS (EI) m/z 244 (Mþ, 21), 199 (43),
182 (60), 129 (100); HRMS 244.0350, C11H7F3O3 required
244.0347.
3446, 1741 cm21 1H NMR (d, d6-DMSO) 3.69 (1H, t,
;
J¼6.4 Hz), 1.85 (1H, td, J¼12.4, 4.5 Hz), 1.60 (1H, td,
J¼12.4, 4.5 Hz), 1.50–1.00 (18H, m); 13C NMR (d, d6-
DMSO) 170.1 (C), 124.8 (CF3, q, 1JC–F¼284 Hz), 77.2 (C,
q, 2JC–F¼27 Hz), 60.9 (CH2), 32.8 (CH2), 32.5 (CH2), 29.3
(CH2), 29.2 (2 CH2), 29.1 (CH2), 29.0 (2 CH2), 25.7 (CH2),
22.5 (CH2); 19F NMR (d, CDCl3) 276.3 (s); MS (EI) m/z
313 (Mþ21, 5), 258 (28), 97 (48), 69 (80), 55 (100); HRMS
313.1638, C14H24F3O4 required 313.1627.
3.3.9. 2-Cyclohexyl-3,3,3-trifluoro-2-hydroxypropanoic
acid (4i). From 800 mg (3.15 mmol) of 3i was obtained
695 mg (98%) of 4i: mp 109–1118C (EtOH); IR (KBr) n
1
3434, 3500–2800, 1747 cm21; H NMR (d, CDCl3) 2.12
(1H, tt, J¼11.0, 2.0 Hz), 2.00–1.00 (10H, m); 13C NMR (d,
CDCl3) 174.5 (C), 123.3 (CF3, 1JC–F¼287 Hz), 80.7 (C, q,
2JC–F¼28 Hz), 40.4 (CH), 26.3 (CH2), 25.8 (CH2), 25.7
(CH2), 25.5 (CH2), 25.4 (CH2); 19F NMR (d, CDCl3) 273.4
(s); MS (EI) m/z 226 (Mþ, 0.2), 181 (3), 144 (16), 83 (100);
HRMS 226.0810, C9H13F3O3 required 226.0817.
3.4. Synthesis of trifluoromethylketones
Pivalaldehyde (75 mL, 0.69 mmol) was added to a solution
of Co(III) complex 1 (7.5 mg, 0.016 mmol) in 1.5 mL of
CH2Cl2. After 5 min of stirring under an O2 atmosphere,
hydroxy acid 4 (0.35 mmol) was added all at once. The
mixture was stirred at room temperature under O2 until
3.3.10. 2-Hydroxy-2-trifluoromethyldodecanoic acid