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T. Yajima et al. / Tetrahedron 61 (2005) 10203–10215
(m, 1H), 2.02 (m, 1H), 2.51 (dq, JZ14.8, 10.4 Hz, 1H,
CF3CHH), 2.66 (dq, JZ14.8, 10.4 Hz, 1H, CF3CHH), 3.46
(s, 1H, OH), 4.74 (dt, JZ4.4, 9.6 Hz, 1H, OCH); 13C NMR
(100 MHz) d 15.9, 21.1, 22.1, 23.1, 26.2, 27.4, 31.4, 34.2,
40.1, 42.6 (q, JC–FZ28.0 Hz, CF3CH2), 46.9, 71.1, 77.3,
125.0 (q, JC–FZ285.1 Hz, CF3), 174.4. More polar
2.06 (m, 2H, CH2), 2.44 (ddd, JZ6.4, 9.8, 12.0 Hz, 1H,
CHH), 2.55 (m, 1H, CHH), 2.71 (m, 1H, CHH), 2.82 (m,
1H, CHH), 3.87 (s, 1H, OH), 4.22 (dq, JZ10.8, 6.8 Hz, 1H,
OCHHCH3), 4.31 (dq, JZ10.8, 6.8 Hz, 1H, OCHHCH3),
7.15–7.30 (m, 5H, arom); 13C NMR (100 MHz) d 14.0, 29.2,
39.0 (t, JC–FZ20.1 Hz, CF2CH2), 42.1, 62.8, 73.6, 126.1,
128.3, 128.4, 140.5, 174.2; IR (neat, cmK1) 3526, 2932,
2986, 1736, 1331, 1196, 1138, 1018, 748, 698; MS m/z 467
(MCKCO2Et, 3%), 436 (26), 408 (14), 361 (2), 91 (7), 58
(100); HRMS calcd for C16H12F13O [MCKCO2Et]
467.0681, found 467.0665.
1
diastereomer. Colorless oil; H NMR (400 MHz) d 0.74
(d, JZ6.8 Hz, 3H, CH3), 0.90 (d, JZ6.0 Hz, 3H, CH3), 0.92
(d, JZ6.0 Hz, 3H, CH3), 0.96–1.09 (m, 4H), 1.46 (s, 3H,
CH3), 1.49 (m, 1H), 1.73 (m, 2H), 1.85 (m, 1H), 2.02 (m,
1H), 2.56 (dq, JZ14.8, 10.4 Hz, 1H, CF3CHH), 2.72 (dq,
JZ14.8, 10.4 Hz, 1H, CF3CHH), 3.50 (s, 1H, OH), 4.78 (dt,
JZ4.4, 9.6 Hz, 1H, OCH); 13C NMR (100 MHz) d 15.7,
4.2.21. Ethyl 4,5,5,5-tetrafluoro-2-hydroxy-2-phenethyl-
4-trifluoromethylnonanoate 41. Colorless oil; H NMR
1
20.9, 22.1, 23.0, 26.0, 27.4, 31.5, 34.2, 40.3, 42.8 (q, JC–F
28.0 Hz, CF3CH2), 47.0, 71.1, 77.3, 125.0 (q, JC–F
285.1 Hz, CF3), 174.5.
Z
Z
(400 MHz) d 1.31 (t, JZ7.2 Hz, 3H, OCH2CH3), 2.05 (m,
2H, CH2), 2.41 (ddd, JZ6.0, 6.0, 13.6 Hz, 1H, CHH), 2.52
(dd, JZ15.6, 24.4 Hz, 1H, CFCHH), 2.73 (dd, 1H, JZ8.2,
15.6 Hz, CFCHH), 2.81 (ddd, JZ5.6, 5.6, 13.6 Hz, 1H,
CHH), 3.63 (s, 1H, OH), 4.24 (dq, JZ13.2, 7.2 Hz, 1H,
OCHHCH3), 4.25 (dq, JZ13.2, 7.2 Hz, 1H, OCHHCH3),
7.14–7.30 (m, 5H, arom); 13C NMR (100 MHz) d 14.0, 29.3,
4.2.18. (1R,2S,5R)-5-Methyl-2-(1-methyl-1-phenylethyl)
cyclohexyl 4,4,4-trifluoro-2-hydroxy-2-methylbutanoate
38. IR (neat, cmK1) 3502, 2959, 1728, 1188, 1153, 702; MS
m/z 267 (MCKC(CH3)2Ph, 3%), 214 (10), 119 (100);
HRMS calcd for C12H18F3O3 [MCKC(CH3)2Ph] 267.1208,
found 267.1239. Less polar diastereomer. Colorless oil; 1H
NMR (400 MHz) d 0.90 (d, JZ6.3 Hz, 3H, CH3), 0.99 (m,
2H, CH2), 1.16 (s, 3H, CH3), 1.19 (m, 1H), 1.22 (s, 3H,
CH3), 1.30 (s, 3H, CH3), 1.50 (m, 1H), 1.71 (m, 1H), 1.82
(m, 1H), 1.97 (m, 1H), 2.11 (dq, JZ15.1, 10.7 Hz, 1H,
CF3CHH), 2.20 (s, 1H, OH), 2.26 (dq, JZ15.1, 10.7 Hz, 1H,
CF3CHH), 2.27 (m, 1H), 4.83 (dt, JZ4.4, 10.3 Hz, 1H,
OCH), 7.26 (m, 2H, arom), 7.33 (m, 3H, arom); 13C NMR
(100 MHz) d 21.8, 23.8, 26.5, 26.6, 29.6, 31.3, 34.6, 39.5,
40.7, 42.0 (q, JC–FZ27.4 Hz, CF3CH2), 49.2, 71.4 (q,
JC–FZ2.7 Hz, CF3CH2C), 77.9, 125.1, 125.2, 126.8 (q,
JC–FZ298.1 Hz, CF3), 128.3, 151.9, 173.3. More polar
diastereomer. Colorless oil; 1H NMR (400 MHz) d 0.89 (d,
JZ6.4 Hz, 3H, CH3), 0.97 (m, 2H, CH2), 1.14 (m, 1H), 1.17
(s, 3H, CH3), 1.22 (s, 3H, CH3), 1.31 (s, 3H, CH3), 1.49 (m,
1H), 1.69 (m, 2H), 1.98 (m, 1H), 2.21 (m, 1H), 2.29 (dq, JZ
15.1, 10.7 Hz, 1H, CF3CHH), 2.40 (dq, JZ15.1, 10.7 Hz,
1H, CF3CHH), 2.65 (s, 1H, OH), 4.87 (dt, JZ4.4, 10.3 Hz,
1H, OCH), 7.19 (m, 2H, arom), 7.30 (m, 3H, arom); 13C
NMR (100 MHz) d 21.8, 25.5, 26.4, 26.9, 28.3, 31.4, 34.5,
39.7, 40.8, 42.1 (q, JC–FZ27.3 Hz, CF3CH2), 49.5, 71.3 (q,
JC–FZ2.7 Hz, CF3CH2C), 78.2, 125.2, 125.4, 126.7 (q,
JC–FZ320.9 Hz, CF3), 128.2, 151.3, 173.8.
36.6 (d, JC–FZ20.1 Hz, CFCH2), 42.1, 62.9, 73.5 (d, JC–F
Z
3.7 Hz, CFCH2CH2), 126.1, 128.3, 128.4, 140.5, 174.0; IR
(neat, cmK1) 3530, 2932, 1740, 1231, 1188, 1161, 1130,
698; MS m/z 390 (MC, 3%), 317 (13), 286 (100), 258 (45),
91 (51); HRMS calcd for C16H17F7O3 [MC] 390.1066,
found 390.1083.
4.2.22. Diethyl 2-hydroxy-2-phenylethylpentanedioate
42. Colorless oil; 1H NMR (400 MHz) d 1.25 (t, JZ
7.2 Hz, 3H, OCH2CH3), 1.30 (t, JZ7.2 Hz, 3H, OCH2CH3),
1.98 (ddd, JZ5.6, 12.0, 14.0 Hz, 1H, CHH), 2.05 (m, 1H,
CHH), 2.08 (m, 2H, CH2), 2.21 (ddd, JZ5.6, 9.6, 15.6 Hz,
1H, CHH), 2.43 (ddd, JZ5.2, 12.0, 14.0 Hz, 1H, CHH),
2.47 (ddd, JZ6.0, 9.6, 15.6 Hz, 1H, CHH), 2.80 (ddd, JZ
5.2, 12.0, 14.0 Hz, 1H, CHH), 3.45 (s, 1H, OH), 4.12 (q, JZ
7.2 Hz, 2H, OCH2CH3), 4.20 (q, JZ7.2 Hz, 2H,
OCH2CH3), 7.17 (m, 3H, arom), 7.27 (m, 2H, arom); 13C
NMR (100 MHz) d 14.2, 14.3, 28.9, 30.0, 34.1, 40.9, 60.5,
62.2, 76.2, 125.8, 128.2, 128.3, 128.4, 173.1, 175.9; IR
(neat, cmK1) 3510, 2982, 2936, 1732, 1454, 1373, 1245,
1188, 1118, 1026, 702; MS m/z 263 (MCKOEt, 8%), 235
(43), 204 (90), 189 (100), 158 (82); HRMS calcd for
C15H19O4 [MCKOEt] 263.1283, found 263.1237.
4.2.23. Ethyl 4-chrolo-2-hydroxy-2-phenethylbutanoate
43. Colorless oil; 1H NMR (400 MHz) d 1.32 (t, JZ7.4 Hz,
3H, OCH2CH3), 1.96 (ddd, JZ5.4 12.2, 13.7 Hz, 1H,
CHH), 2.08 (ddd, JZ5.4, 13.7, 13.7 Hz, 1H, CHH), 2.21
(ddd, JZ4.9, 7.8, 13.7 Hz, 1H, CHH), 2.30 (m, 1H, CHH),
2.41 (ddd, JZ4.9, 11.7, 11.7 Hz, 1H, CHH), 2.78 (ddd, JZ
4.9, 11.7, 11.7 Hz, 1H, CHH), 3.51 (s, 1H, OH), 3.56 (m,
1H, CHH), 3.62 (ddd, JZ4.9, 8.7, 11.7 Hz, 1H, CHH), 4.23
(q, JZ7.4 Hz, 2H, OCH2CH3), 7.15–7.30 (m, 5H, arom);
13C NMR (100 MHz) d 14.3, 29.7, 39.4, 41.4, 41.8, 62.5,
4.2.19. Ethyl 4,4,5,5,5-pentafluoro-2-hydroxy-2-phene-
thylpentanoate 39. Colorless oil; H NMR (400 MHz) d
1
1.31 (t, JZ6.8 Hz, 3H, OCH2CH3), 2.07 (m, 2H, CH2), 2.44
(m, 1H, CHH), 2.57 (m, 1H, CHH), 2.66 (m, 1H, CHH),
2.81 (ddd, 1H, JZ5.8, 10.7, 13.6 Hz, CHH), 3.63 (s, 1H,
OH), 4.21 (dq, JZ10.7, 6.8 Hz, 1H, OCHHCH3), 4.30 (dq,
JZ10.7, 6.8 Hz, 1H, OCHHCH3), 7.14–7.30 (m, 5H, arom);
13C NMR (100 MHz) d 14.1, 29.3, 38.1 (t, JC–FZ19.2 Hz,
CF2CH2), 42.0, 62.8, 73.4 (t, JC–FZ1.8 Hz, CF2CH2C),
126.1, 128.3, 128.4, 140.6, 174.2; IR (neat, cmK1) 3524,
2986, 1740, 1238, 1196, 1146, 702; MS m/z 340 (MC, 3%),
267 (11), 236 (100), 208 (53), 91 (63); HRMS calcd for
C15H17F5O3 [MC] 340.1098, found 340.1107.
75.4, 126.0, 128.3, 128.4, 141.0, 175.7; IR (neat, cmK1
)
3531, 2932, 1732, 1454, 1246, 4496, 745, 698; MS m/z 199
(MCKCO2Et, 11%), 197 (33), 168 (24), 166 (70), 168 (24),
105 (12), 91 (100); HRMS calcd for C11H14ClO [MCK
CO2Et] 197.0734, found 197.0713.
4.2.20. Ethyl 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-2-
hydroxy-2-phenethylnonanoate 40. Colorless oil; 1H
NMR (400 MHz) d 1.31 (t, JZ6.8 Hz, 3H, OCH2CH3),
4.2.24. Ethyl 2-hydroxy-4-iodo-2-phenethylbutanoate
44. Colorless oil; 1H NMR (400 MHz) d 1.32 (t, JZ7.3 Hz,