8534
M. Yus et al. / Tetrahedron 59 (2003) 8525–8542
J¼6.6 Hz, 1H, CHOH), 4.68 (s, 2H, CH2v), 7.29 (m, 5H,
ArH); dC 13.8 (CH3), 20.8, 25.5, 27.6, 35.8, 38.1, 38.9
(6£CH2), 74.5 (CHOH), 108.6 (CH2v), 125.8, 127.3,
128.3, 144.8 (6C, ArC), 149.7 (CvCH2); m/z 232 (Mþ,
0.1%), 214 (Mþ218, 3.6%), 133 (13), 130 (32), 117 (10),
110 (24), 107 (100), 105 (12), 91 (11), 79 (56), 77 (28), 55
(19). HRMS: Mþ, found 232.1834. C16H24O requires
232.1827.
4.4.2. Lithiation of compound 9. To a stirred green
suspension of lithium powder (40 mg, 5.8 mmol) and DTBB
(26.6 mg, 0.1 mmol) in THF (4 mL) at 2788C was added
(Z)-8-chlorooct-3-ene (9; 0.146 g, 1.0 mmol) under an
argon atmosphere. The colour disappeared after the
substrate addition, the reaction mixture was stirred until
the green colour was recovered (ca. 40 min) and the
corresponding electrophile (1.1 mmol) was then added.
The resulting mixture was stirred for 15 min at the same
temperature (2788C), then it was hydrolysed with 2 M HCl
(5 mL) and stirred to room temperature for 10 min.
The reaction mixture was extracted with diethyl ether
(3£15 mL), the organic phase was dried over anhydrous
magnesium sulphate and the solvents were concentrated
under vacuum (15 Torr). Compounds 11 were isolated after
column chromatography (silica gel, hexane/ethyl acetate
mixtures). Yields are given in Table 4; physical, spectro-
scopic and analytical data follows.
4.4.2.1. (Z)-3-Ethylundec-8-en-3-ol (11a). Rf 0.4 (hexane/
ethyl acetate: 9/1); n (film) 3415 (OH), 3005 cm21 (CvC);
dH 0.86 (t, J¼7.6 Hz, 6H, 2£COHCH2CH3), 0.96 (t, J¼
7.5 Hz, 3H, CHCH2CH3), 1.31 (m, 7H, CH2CH2CH2COH),
1.46 (q, J¼7.5 Hz, 4H, 2£CH2CH3), 2.04 (m, 4H,
CH2CHvCHCH2), 5.35 (m, 2H, CHvCH); dC 7.7
(2£CH2CH3), 14.3 (CH3), 20.5, 23.0, 27.0, 30.4, 30.9,
38.1 (7£CH2), 74.6 (COH), 129.0 (vCHCH2CH2), 131.7
(vCHCH2CH3); m/z 180 (Mþ218, 1.1%), 169 (15), 151
(17), 110 (19), 109 (14), 97 (13), 96 (10), 95 (23), 87 (93),
85 (12), 82 (14), 81 (17), 69 (23), 67 (19), 57 (100), 55 (39).
HRMS: Mþ2[H2O], found 180.1868. C13H24 requires
180.1878.
4.4.2.2. (Z)-2,2-Dimethylundec-8-en-3-ol (11b). Rf 0.4
(hexane/ethyl acetate: 9/1); n (film) 3393 (OH), 3005,
1463 cm21 (CvC); dH 0.89 (s, 9H, C(CH3)3), 1.91 (t, J¼
7.5 Hz, 3H, CH3), 1.39 (m, 7H, 3£CH2 and OH), 2.04
(m, 4H, CH2CHvCHCH2), 3.18 (dd, J¼10.2 Hz, 1.5, 1H,
CHOH), 5.35 (m, 2H, CHvCH); dC 14.3 (CH3), 20.4, 26.6,
27.0, 29.7, 31.3 (5£CH2), 25.6 [3C, C(CH3)3], 34.8
[C(CH3)3], 79.8 (CHOH), 129.0 (vCHCH2CH2), 131.5
(vCHCH2CH3); m/z 180 (Mþ218, 3.1%), 141 (12), 137
(15), 124 (14), 123 (26), 110 (31), 109 (22), 97 (15), 96 (22),
95 (29), 87 (20), 85 (10), 83 (19), 82 (49), 81 (100), 71 (25),
70 (15), 69 (39), 68 (14), 67 (69), 57 (82), 56 (12), 55 (75),
54 (12), 53 (11). HRMS: Mþ2[H2O], found 180.1876.
C13H24 requires 180.1878.
4.3.2.4. 1-(5-Propylhex-5-enyl)cyclohexanol (8d). Rf
0.3 (hexane/ethyl acetate: 9/1); n (film) 3385 (OH), 3076,
1644 cm21 (CvC); dH 0.90 (t, J¼7.3 Hz, 3H, CH3), 1.43
(m, 19H, 9£CH2 and OH), 2.00 [m, 4H, CH2C(vCH2)-
CH2], 4.69 (s, 2H, CH2v); dC 13.8 (CH3), 20.8, 22.2, 22.6,
25.8, 28.3, 36.0, 37.3, 38.1, 42.3 (11£CH2), 71.3 (COH),
108.6 (CH2v), 149.7 (Cv); m/z 206 (Mþ218, 1.8%), 135
(12), 123 (18), 122 (52), 111 (11), 110 (94), 109 (18), 108
(10), 107 (18), 99 (89), 97 (10), 96 (11), 95 (100), 94 (13),
93 (21), 83 (17), 82 (14), 81 (84), 80 (10), 79 (33), 69 (27),
68 (14), 67 (41), 57 (11), 56 (14), 55 (75), 53 (16). HRMS:
Mþ2[H2O], found 206.2039. C15H26 requires 206.2035.
4.3.2.5. 2-Phenyl-7-propyloct-7-en-2-ol (8e). Rf 0.3
(hexane/ethyl acetate: 9/1); n (film) 3416 (OH), 3083,
3064, 3026, 1644 cm21 (CvC); dH 0.87 (t, J¼7.3 Hz, 3H,
CH2CH3), 1.28 (m, 7H, 3£CH2 and OH), 1.54 (s, 3H,
COHCH3), 1.81 (m, 2H, CH2), 1.93 [t, J¼7.41 Hz, 4H,
CH2C(vCH2)CH2], 4.64 (s, 2H, CH2v), 7.22, 7.32, 7.42
(3m, 5H, ArH); dC 13.8 (CH3), 20.8, 23.7, 28.1, 35.8, 38.1,
44.0 (6£CH2), 30.4 (CH3COH), 74.6 (COH), 108.6
(CH2v), 124.7, 126.4, 128.0, 148.0 (6C, ArC), 149.7
(Cv); m/z 246 (Mþ, 0.03%), 228 (Mþ218, 2.0%), 144
(33), 131 (25), 129 (56), 121 (100), 118 (28), 117 (16), 115
(14), 105 (16), 91 (22), 77 (11), 55 (13). HRMS: Mþ, found
246.2011. C17H26O requires 246.1984.
4.3.2.6. Trimethyl(5-propylhex-5-enyl)silane (8f). Rf
0.8 (hexane); n (film) 3071, 1644 cm21 (CvC); dH 0.00
[s, 9H, Si(CH3)3], 0.52 (t, J¼8.3 Hz, 2H, CH2Si), 0.93
(t, J¼7.3 Hz, 3H, CH3), 1.32 (m, 2H, CH2), 1.46 (m, 4H,
2£CH2), 2.00 [m, 4H, CH2C(vCH2)CH2], 4.72 (s, 2H,
CH2vC); dC 21.65 [3C, Si(CH3)3], 13.9 (CH3), 16.6, 20.9,
23.7, 31.7 (4£CH2), 35.8, 38.2 [CH2C(vCH2)CH2], 108.5
(CH2v), 150.1 (CvCH2); m/z 198 (Mþ, 0.03%), 114 (25),
73 (100), 59 (17). HRMS: Mþ2[CH3], found 183.1572.
C11H23Si requires 183.1569.
4.4. DTBB-catalysed lithiation of (Z)-8-chloro-3-octene
(9)
4.4.2.3. (Z)-1-Phenylnon-6-en-1-ol (11c). Rf 0.2 (hexane/
ethyl acetate: 9/1); n (film) 3371 (OH), 3085, 3062, 3027,
3003, 1602, 1493 cm21 (CvC); dH 0.93 (t, J¼7.6 Hz, 3H,
CH3), 1.33 (m, 4H, 2£CH2), 1.72 (m, 2H, CH2), 2.01 (m,
4H, CH2CHvCHCH2), 2.34 (s, 1H, OH), 4.61 (t, J¼6.6 Hz,
1H, CHOH), 5.33 (m, 2H, CHvCH), 7.29 (m, 5H, ArH); dC
14.3 (CH3), 20.4, 25.4, 26.9, 29.6, 38.9 (5£CH2), 74.6
(CHOH), 125.8, 127.4, 128.3, 144.8 (6C, ArC), 128.9
(vCHCH2CH2), 131.7 (vCHCH2CH3); m/z 219 (Mþþ1,
0.20%), 218 (Mþ, 1.22%), 144 (15), 133 (15), 130 (12), 117
(11), 107 (100), 105 (13), 104 (12), 91 (11), 79 (52), 77 (25).
HRMS: Mþ, found 218.1658. C15H22O requires 218.1671.
4.4.2.4. 1-[(Z)-Oct-5-enyl]-1-cyclohexanol (11d). Rf 0.3
(hexane/ethyl acetate: 9/1); n (film) 3383 (OH), 3004,
1462 cm21 (CvC); dH 0.96 (t, J¼7.5 Hz, 3H, CH3), 1.50
(m, 17H, 8£CH2 and OH), 2.04 (m, 4H, CH2CHvCHCH2),
5.35 (m, 2H, CHvCH); dC 14.3 (CH3), 20.4, 22.2, 22.5,
25.8, 27.0, 30.3, 37.3, 42.2 (10£CH2), 71.4 (COH), 129.0
4.4.1. Preparation of compound 9.29 A mixture of (Z)-5-
octen-1-ol (15.4 mL, 100 mmol) and triphenylphospane
(28.87 g, 110 mmol) in carbon tetrachloride was refluxed
for 48 h. Then, the reaction mixture was concentrated under
vacuum (15 Torr) and the residue was purified by column
chromatography (silica gel, hexane) to give 14.7 g of
compound 9 (99%).
4.4.1.1. (Z)-8-Chlorooct-3-ene (9).51 Rf 0.7 (hexane); n
(film) 3005, 1655 cm21 (CvC); dH 0.96 (t, J¼7.5 Hz, 3H,
CH3), 1.49 (m, 2H, CH2), 1.78 (m, 2H, CH2), 2.04 (m, 4H,
CH2CHvCHCH2), 3.53 (t, J¼6.6 Hz, 2H, CH2Cl), 5.35
(m, 2H, CHvCH); dC 14.3 (CH3), 20.5, 26.2, 26.9, 32.1
(4£CH2), 44.9 (CH2Cl), 128.2 (vCHCH2CH2), 132.2
(vCHCH2CH3); m/z 148 (Mþþ2, 9.4%), 146 (Mþ,
29.2%), 104 (26), 91 (10), 81 (36), 70 (13), 69 (53), 68
(37), 67 (30), 56 (45), 55 (100), 54 (16), 53 (19).