4914
M. Yus et al. / Tetrahedron 58 -2002) 4907±4915
ArCH), 4.84 +1H, d, J8.5 Hz, CHOH), 6.24 +1H, d,
J3.1 Hz, HCvCHO), 6.33 +1H, dd, J3.1, 1.8 Hz,
HCvCHO), 7.23±7.41 +6H, m, ArH, HCvCO); dC 34.9
+CH2CH2OH), 48.3 +ArCH), 60.8 +CH2OH), 71.8 +CHOH),
107.8, 110.2, 127.3, 128.6, 128.8, 140.4, 142.1, 154.7 +ArC,
OCvCHCHvCHO); m/z 214 +M12H2O, 5%), 118 +79),
117 +66), 97 +100); HRMS: M12H2O, found 214.0988.
C14H14O2 requires 214.0994. Minor isomer: colourless oil;
n +®lm) 3403 +OH), 3055 +ArH), 1266 cm21 +C±O); dH 1.62
+2H, br s, 2OH), 1.99±2.09 +1H, m, CHHCH2OH), 2.21±
2.32 +1H, m, CHHCH2OH) 3.26±3.33 +1H, m, ArCH),
3.48±3.68 +2H, m, CH2OH), 4.85 +1H, d, J7.5 Hz,
CHOH), 6.01 +1H, d, J3.3 Hz, HCvCHO), 6.19 +1H,
dd, J3.3, 1.8 Hz, HCvCHO), 7.12±7.29 +6H, m, ArH,
HCvCO); dC 34.4 +CH2CH2OH), 48.4 +ArCH), 61.2
+CH2OH), 72.1 +CHOH), 106.9, 110.0, 126.7, 128.2,
128.4, 141.3, 141.6, 155.1 +ArC, OCvCHCHvCHO),
m/z 214 +M12H2O, 4%), 118 +81), 117 +68), 97 +100);
HRMS: M12H2O, found 214.0987. C14H14O2 requires
214.0994.
9.16]; n +KBr) 3381 +OH), 3084, 3059, 3026 +ArH),
1265 cm21 +C±O); dH 1.55±1.80+8H, m, 4CH ), 2.03±
2
2.18 +2H, m, CH2), 2.79 +1H, dd, J10.1, 4.8 Hz, ArCH),
3.05 +2H, br s, 2OH), 3.33±3.41 +1H, m, CHHOH), 3.53
+1H, ddd, J10.7, 6.6, 5.0 Hz, CHHOH), 7.20±7.32 +5H, m,
ArH); dC 23.3, 23.6, 33.4, 38.5, 39.2 +CH2), 51.8 +ArCH),
61.2 +CH2OH), 84.6 +COH), 126.6, 128.2, 129.0, 141.7
+ArC); m/z 202 +M12H2O, 1.8%), 118 +100), 117 +57).
4.4.11. 1-*3-Hydroxy-1-phenylpropyl)cyclohexanol *11i).
White solid, mp 119±1208C +pentane/dichloromethane);
[Found: C, 76.21; H, 9.46. C15H22O2 requires C, 76.87; H,
9.47]; n +KBr) 3333 +OH), 3082, 3060, 3024 +ArH),
1275 cm21 +C±O); dH 1.07±1.71 +10H, m, 5CH2), 1.93±
2.22 +4H, m, CH2, 2OH), 2.72 +1H, dd, J11.0, 3.7 Hz,
ArCH), 3.29±3.37, 3.47±3.54 +2H, 2m, CH2OH), 7.22±
7.31 +5H, m, ArH); dC 21.7, 21.9, 25.6, 31.8, 35.1, 35.8
+CH2), 53.0+ArCH), 61.4 +CH OH), 73.0+COH), 126.5,
2
128.1, 129.6, 141.1 +ArC); m/z 234 +M1, 0.5%), 118
+100), 117 +57), 99 +96), 81 +69).
4.4.12. *1R,2S,5R)-1-*3-Hydroxy-1-phenylpropyl)-2-iso-
propyl-5-methylcyclohexanol *11j). Major isomer: colour-
less oil; n +®lm) 3394 +OH), 3086, 3053, 3028 +ArH),
1265 cm21 +C±O); dH 0.69 +3H, d, J6.8 Hz, CHCH3),
0.89 +3H, d, J6.4 Hz, CH3CHCH3), 0.92 +3H, d,
J6.8 Hz, CH3CHCH3), 1.18±1.41 +4H, m, CH2, 2CH),
1.62±1.66 +2H, m, CH2), 1.79±1.96 +2H, m, CH2), 2.24±
2.33 +4H, m, CH2, 2OH), 2.44±2.53 +1H, m, CH), 3.35 +1H,
dd, J3.9, 3.7 Hz, ArCH), 3.33±3.43 +1H, m, CHHOH),
3.56 +1H, ddd, J10.7, 6.3, 4.4 Hz, CHHOH), 7.19±7.28
+5H, m, ArH); dC 18.4 +CH3), 21.2 +CH2), 22.6, 22.8 +CH3),
25.0, 28.0 +CH), 33.0, 34.4, 41.4 +CH2), 45.8, 49.7 +CH),
61.8 +CH2OH), 78.1 +COH), 126.4, 128.0, 129.6, 141.7
+ArC); m/z 290+M 1, 0.5%), 155 +100), 118 +57), 81 +95),
55 +51), 43 +62), 41 +67); HRMS: M1, found 290.2247.
C19H30O2 requires 290.2246. Minor isomer: colourless oil;
n +®lm) 3404 +OH), 3085, 3054, 3030 +ArH), 1265 cm21
+C±O); dH 0.70 +3H, d, J7.0Hz, C HCH3), 0.90 +3H, d,
J6.3 Hz, CH3CHCH3), 0.93 +3H, d, J6.8 Hz,
CH3CHCH3), 1.18±1.98 +13H, m, 4CH2, 3CH, 2OH),
2.24±2.35 +1H, m, CHHCH2OH, 2.45±2.54 +1H, m,
CHHCH2OH), 3.33 +1H, dd, J10.1, 4.2 Hz, ArCH), 3.44
+1H, ddd, J10.8, 8.5, 5.5 Hz, CHHOH), 3.57 +1H, ddd,
J10.8, 6.6, 4.7 Hz, CHHOH), 7.21±7.29 +5H, m, ArH);
dC 18.4 +CH3), 21.2 +CH2), 22.6, 22.8 +CH3), 25.0, 28.1
+CH), 33.2, 34.4, 41.5 +CH2), 45.8, 49.9 +CH), 62.3
+CH2OH), 78.1 +COH), 126.4, 128.1, 129.5, 141.8 +ArC);
m/z 290+M 1, 0.5%), 155 +87), 118 +57), 81 +100), 43 +56),
41 +64); HRMS: M1, found 290.2250. C19H30O2 requires
290.2246.
4.4.7. 4-Methyl-3-phenyl-1,4-pentanediol *11e). White
solid, mp .3008C +pentane/dichloromethane); [Found: C,
74.12; H, 9.25. C12H18O2 requires C, 74.18; H, 9.34]; n
+KBr) 3384 +OH), 3084, 3054, 3029 +ArH), 1265 cm21
+C±O); dH 1.16 +3H, s, CH3), 1.17 +3H, s, CH3), 1.93±
2.27 +2H, m, CH2), 2.36 +2H, br s, 2OH), 2.76 +1H, dd,
J10.4, 4.0 Hz, ArCH), 3.33±3.58 +2H, m, CH2OH),
7.20±7.32 +4H, m, ArH); dC 27.0, 28.7 +CH3), 32.7 +CH2),
53.7 +ArCH), 61.4 +CH2OH), 72.7 +COH), 126.7, 128.2,
129.3, 141.3 +ArC); m/z 176 +M12H2O, 1%), 118 +100),
117 +96), 59 +87), 43 +55).
4.4.8. 4-Pentyl-3-phenyl-1,4-nonanediol *11f). Colourless
oil; n +®lm) 3403 +OH), 3084, 3058, 3027 +ArH), 1265 cm21
+C±O); dH 0.84 +3H, t, J7.2 Hz, CH3), 0.90 +3H, t,
J6.8 Hz, CH3), 1.12±1.34 +14H, m, 7CH2), 1.51±1.54
+2H, m, CH2), 1.74 +2H, br s, 2OH), 1.98±2.06 +2H, m,
ArCHCH2), 2.82 +1H, dd, J9.9, 5.0Hz, ArCH), 3.29
+1H, td, J10.9, 7.4 Hz, CHHOH), 3.46 +1H, td, J10.9,
5.5 Hz, CHHOH), 7.19±7.29 +5H, m, ArH); dC 14.0, 14.0
+CH3), 22.5, 22.6, 23.0, 23.2, 32.1, 32.3, 32.5, 36.4, 37.3
+CH2), 49.3 +ArCH), 61.3 +CH2OH), 76.0+COH), 126.5,
128.1, 129.6, 141.0+ArC); m/z 288 +M12H2O, 0.38%),
171 +99), 118 +74), 55 +70), 43 +100), 41 +62); HRMS:
M12H2O, found 288.2440. C20H32O requires 288.2453.
4.4.9. 1,1,2,-Triphenyl-1,4-butanediol *11g). White solid,
mp 228±2308C +pentane/dichloromethane); [Found: C,
82.57; H, 6.95. C22H22O2 requires C, 82.98; H, 6.97]; n
+KBr) 3370 +OH), 3085, 3055, 3025 +ArH), 1260 cm21
+C±O); dH 2.03±2.07 +2H, m, CH2CH2OH), 2.79 +2H, br
s, 2OH), 3.34±3.42, 3.51±3.58 +2H, 2m, CH2OH), 4.02 +1H,
t, J7.3 Hz, ArCH), 6.98±7.15 +7H, m, ArH), 7.22±7.26
+4H, m, ArH), 7.36 +2H, t, J7.6 Hz, ArH), 7.63 +2H, d,
J7.3 Hz, ArH); dC 33.3 +CH2CH2OH), 50.3 +ArCH), 60.9
+CH2OH), 80.7 +COH), 125.7, 126.2, 126.3, 126.6, 126.8,
127.6, 128.0, 128.3, 130.1, 139.5, 145.9, 146.2 +ArC); m/z
300 +M12H2O, 2%), 118 +100), 117 +62).
4.5. Reductive opening of 2,3-benzofuran *12)19
Isolation of 2-vinylphenol -14). To a blue suspension of
lithium powder +140mg, 20mmol) and a catalytic amount
of DTBB +50mg, 0.19 mmol; 5% molar) in THF +4 mL)
was added 2,3-benzofuran +12, 236 mg, 0.22 mL,
2.0mmol) at 0 8C and the resulting mixture was stirred for
45 min at the same temperature. Then, it was cooled down at
2788C and 0.5 mL of H2O was added and after 15 min it
was hydrolysed with 3N hydrochloric acid. The reaction
mixture was allowed to reach the ambient temperature and
4.4.10. 1-*3-Hydroxy-1-phenylpropyl)cyclopentanol *11h).
White solid, mp 93±948C +pentane/dichloromethane);
[Found: C, 76.25; H, 9.22. C14H20O2 requires C, 76.31; H,