2
22
Can. J. Chem. Vol. 82, 2004
1
1
5
1
0.7 Hz, 1H), 4.35 (d, J = 11.5 Hz, 1H), 4.39 (d, J =
1.5 Hz, 1H), 4.64 (s, 1H), 4.81 (dd, J = 10.7, 2.5 Hz, 1H),
.01 (s, 1H), 5.13 (dd, J = 11.1, 1.1 Hz, 1H), 5.34 (dd, J =
(s, 9H), 0.95 (s, 9H), 1.74 (s, 3H), 1.79 (s, 3H), 1.83 (s, 3H),
2.09 (d, J = 14.4 Hz, 1H), 2.91 (dd, J = 14.4, 9.8 Hz, 1H),
3.20 (s, 3H), 4.35 (m, 1H), 4.49 (s, 2H), 4.83 (s, 1H), 5.12
(s, 1H), 5.13 (d, J = 11.1 Hz, 1H), 5.48 (d, J = 17.3 Hz, 1H),
6.83 (dd, J = 17.3, 11.1 Hz, 1H). C NMR (CDCl3,
125 MHz) δ: –5.1, 2.6, 18.4, 20.5, 22.1, 22.9, 26.1, 38.3,
57.1, 58.4, 81.9, 114.2, 114.9, 127.4, 127.9, 128.3, 134.0,
138.1, 146.9.
1
3
7.3, 1.1 Hz, 1H), 6.62 (dd, J = 17.3, 11.1 Hz, 1H).
C
1
3
NMR (CDCl , 125 MHz) δ: –5.2, 2.5, 18.2, 20.3, 21.9, 22.7,
3
2
1
5.9, 38.4, 58.8, 72.0, 114.1, 115.0, 128.9, 133.2, 137.9,
46.1, 146.2, 146.8. HR-MS (EI) m/z calcd. for C H OSi
2
3
42
+
(
[M – H O]): 390.2274; found: 390.2770.
2
3
-(tert-Butyl-dimethyl-silanyloxymethyl)-7-isopropenyl-8-
3-(tert-Butyl-dimethyl-silanyloxymethyl)-7-isopropenyl-5-
methyl-nona-1,3,7-trien-5-ol (14c)
methoxy-8-methylnona-1,3,7-triene (15c)
–
1
–1
7
8% from 7c. IR (neat) (cm ) ν: 3432, 3075, 2954, 2929,
89% from 14c. IR (neat) (cm ) ν: 2956, 2929, 2858,
1
1
2
3
1
2
8
1
1
1
5
857, 1631, 1607. H NMR (CDCl , 500 MHz) δ: 0.06 (s,
1615. H NMR (CDCl , 500 MHz) δ: 0.06 (s, 6H), 0.87 (s,
3
3
H), 0.07 (s, 3H), 0.87 (s, 9H), 1.69 (s, 3H), 1.72 (s, 3H),
.77 (s, 3H), 2.24 (dd, J = 13.9, 5.3 Hz, 1H), 2.28 (s, 1H),
.50 (dd, J = 13.9, 8.3 Hz, 1H), 4.25 (s, 2H), 4.57 (ddd, J =
.3, 8.1, 5.3 Hz, 1H), 4.58 (s, 1H), 4.97 (s, 1H), 5.05 (d, J =
1.0 Hz, 1H), 5.31 (d, J = 17.6 Hz, 1H), 5.62 (d, J = 8.1 Hz,
9H), 1.65 (s, 3H), 1.66 (s, 3H), 1.75 (s, 3H), 2.17 (dd, J =
14.1, 5.9 Hz, 1H), 2.51 (dd, J = 14.1, 7.4 Hz, 1H), 3.19 (s,
3H), 4.08 (ddd, J = 9.2, 7.4, 5.9 Hz, 1H), 4.22 (d, J =
11.3 Hz, 1H), 4.31 (d, J = 11.3 Hz, 1H), 4.56 (s, 1H), 4.95
(s, 1H), 5.06 (d, J = 11.0 Hz, 1H), 5.37 (d, J = 17.6 Hz, 1H),
5.41 (d, J = 9.2 Hz, 1H), 6.26 (dd, J = 17.6, 11.0 Hz, 1H).
1
3
H), 6.24 (dd, J = 17.6, 11.0 Hz, 1H). C NMR (CDCl3,
25 MHz) δ: –5.4 (2), 18.2, 20.1, 21.8, 22.5, 25.8, 38.4,
1
3
C NMR (CDCl , 125 MHz) δ: –5.4, 18.3, 20.2, 21.9, 22.6,
3
8.1, 66.6, 113.6, 113.9, 129.2, 132.4, 136.4, 138.4, 146.2.
25.9, 37.3, 56.3, 57.9, 75.8, 113.7, 113.9, 127.7, 132.5,
+
HR-MS (EI) m/z calcd. for C H OSi ([M – H O]):
134.7, 138.3, 139.5, 146.4. HR-MS (EI) m/z calcd. for
2
0
34
2
+
3
18.2379; found: 318.2383.
C H O Si ([M] ): 350.2641; found: 350.2642.
2
1
38
2
General procedure for methylation of the secondary
alcohols
General procedure for deprotection of the primary
alcohols
Sodium hydride (3.0 equiv., 60% dispersion in mineral
oil) was added to a solution of the alcohol (1.0 equiv.) in
Tetrabutylammonium fluoride (1.5 equiv., 1.0 mol L–1 in
THF) was added to a solution of silane (1.0 equiv.) in THF
–
1
–1
THF ([alcohol] = 1.0 mol L ) at 0 °C. After 30 min,
iodomethane (20.0 equiv.) was added, and the solution was
stirred for 18 h at 21 °C. A saturated aqueous solution of
([silane] = 1.0 mol L ) at 0 °C, and the resulting solution
was stirred for 18 h at 21 °C. A saturated aqueous solution
of NH Cl was then added; the layers were separated, and the
4
NH Cl was subsequently added; the layers were separated,
and the aqueous layer was extracted with dichloromethane.
The combined organic extracts were washed with brine,
aqueous layer was extracted with ether. The combined or-
4
ganic extracts were washed with brine, dried (MgSO ), fil-
4
tered, and concentrated under reduced pressure. The crude
material was purified by flash chromatography (silica gel,
ether – petroleum ether).
dried (MgSO ), filtered, and concentrated under reduced
4
pressure. The crude material was purified by flash chroma-
tography (silica gel, ether – petroleum ether).
6
-Isopropenyl-4-methoxy-3,7-dimethyl-2-vinyl-octa-2,6-
3
-(tert-Butyl-dimethyl-silanyloxymethyl)-7-isopropenyl-5-
dien-1-ol (16a)
–
1
hydroxy-8-methyl-4-methyl-nona-1,3,7-triene (15a)
99% from 15a. IR (neat) (cm ) ν: 3445, 2922, 1629,
–
1
1
9
1% from 14a. IR (neat) (cm ) ν: 2929, 2858, 1633,
1444, 1364, 1099, 996, 898, 691, 630. H NMR (CDCl ,
3
1
1
463, 1383, 1255, 1100, 1068, 898, 851, 837, 774. H NMR
500 MHz) δ: 1.65 (s, 6H), 1.66 (s, 3H), 1.72 (s, 3H), 2.18
(dd. J = 14.1, 5.9 Hz, 1H), 2.67 (dd, J = 14.1, 7.6 Hz, 1H),
3.00 (s, 3H), 4.29–4.40 (m, 3H), 4.72 (s, 1H), 4.99 (s, 1H),
5.10 (d, J = 11.1 Hz, 1H), 5.44 (d, J = 17.7 Hz, 1H), 6.59
(dd, J = 17.7, 11.1 Hz, 1H). C NMR (CDCl , 125 MHz) δ:
12.2, 20.1, 22.0, 22.7, 36.0, 56.0, 57.4, 79.1, 114.1, 114.2,
(
CDCl , 500 MHz) δ: 0.11 (s, 6H), 0.96 (s, 9H), 1.73 (s,
3
3
H), 1.74 (s, 3H), 1.79 (s, 3H), 1.82 (s, 3H), 2.11 (dd, J =
4.2, 4.3 Hz, 1H), 2.79 (dd, J = 14.2, 8.9 Hz, 1H), 3.13 (s,
H), 4.30 (d, J = 11.2 Hz, 1H), 4.48 (dd, J = 8.9, 4.3 Hz,
H), 4.74 (d, J = 11.2 Hz, 1H), 4.81 (s, 1H), 5.09 (s, 1H),
.16 (dd, J = 11.2, 1.1 Hz, 1H), 5.50 (dd, J = 17.5, 1.1 Hz,
H), 6.69 (dd, J = 17.5, 11.2 Hz, 1H). 13C NMR (CDCl3,
25 MHz) δ: –5.2, 12.2, 18.5, 20.2, 22.1, 22.9, 26.1, 36.2,
1
3
1
5
1
1
5
1
1
3
3
128.5, 133.8, 134.5, 134.9, 139.3, 146.8. HR-MS (EI) m/z
calcd. for C H O ([M] ): 250.1934; found: 250.1938.
+
16
26
2
6.3, 57.9, 79.1, 114.0, 127.6, 128.3, 133.5, 133.9, 135.0,
6
-Isopropenyl-4-methoxy-7-methyl-3-trimethylsilanyl-2-
+
39.1, 147.0. HR-MS (EI) m/z calcd. for C H O Si ([M] ):
2
2
40
2
vinyl-octa-2,6-dien-1-ol (16b)
–
1
3
64.2799; found: 364.2801. Anal calcd. for C H O Si (%):
22 40 2
83% from 15b. IR (neat) (cm ) ν: 3415, 2910, 2858,
1
C 72.97, H 11.06; found: C 73.13, H 11.06.
2
1
816, 1631. H NMR (CDCl , 300 MHz) δ: 0.23 (s, 9H),
3
.66 (s, 3H), 1.69 (s, 3H), 1.76 (s, 3H), 1.93 (dd, J = 7.6,
3
-(tert-Butyl-dimethyl-silanyloxymethyl)-7-isopropenyl-5-
methoxy-8-methyl-4-trimethylsilanyl-nona-1,3,7-triene
15b)
5% from 14b. IR (neat) (cm ) ν: 2956, 2858, 1630. H
NMR (CDCl , 500 MHz) δ: 0.10 (s, 3H), 0.11 (s, 3H), 0.38
4.5 Hz, 1H), 2.07 (dd, J = 14.5, 4.5 Hz, 1H), 2.71 (dd, J =
14.5, 8.6 Hz, 1H), 3.17 (s, 3H), 4.22 (dd, J = 8.6, 4.5 Hz,
1H), 4.32 (dd, J = 12.1, 7.6 Hz, 1H), 4.45 (dd, J = 12.1,
4.5 Hz, 1H), 4.61–4.63 (m, 1H), 4.99–5.02 (m, 1H), 5.20
(dd, J = 11.1, 0.8 Hz, 1H), 5.43 (dd, J = 17.3, 0.8 Hz, 1H),
(
–
1
1
9
3
©
2004 NRC Canada