6560 J . Org. Chem., Vol. 61, No. 19, 1996
Wipf and Xu
cm-1; 1H NMR δ 7.69-7.66 (m, 4 H), 7.45-7.35 (m, 6 H), 6.44
(d, 1 H, J ) 17.2 Hz), 6.37 (d, 1 H, J ) 10.9 Hz), 6.03 (d, 1 H,
J ) 11.1 Hz), 5.73 (dt, 1 H, J ) 15.0, 7.1 Hz), 5.18 (d, 1 H, J
) 17.2 Hz), 5.00 (d, 1 H, J ) 10.6 Hz), 3.68 (t, 2 H, J ) 6.3
Hz), 2.27 (q, 2 H, J ) 7.3 Hz), 1.85 (s, 3 H), 1.68 (p, 2 H, J )
6.8 Hz), 1.06 (s, 9 H); 13C NMR δ 141.5, 135.7, 134.1, 133.3,
131.6, 129.6, 127.7, 127.1, 111.9, 63.2, 32.3, 29.5, 26.9, 19.3,
12.0; MS (EI) m/z (relative intensity) 333 ([M - C4H9]+); HRMS
(EI) m/z calcd for C22H25OSi (M - C4H9) 333.1674, found
333.1670.
16.6; MS (EI) m/z (relative intensity) 476 (M+); HRMS (EI)
m/z calcd for C31H44O2Si 476.3111, found: 476.3138.
(4E,6E,10R)-10-Meth oxy-7-m eth yltr id eca -4,6,12-tr ien -
1-ol. To a solution of 380 mg (0.80 mmol) of tert-butyl-(4E,6E,-
10R)-[(10-methoxy-7-methyltrideca-4,6,12-trienyl)oxy]diphen-
ylsilane in 8 mL of THF was added dropwise 0.96 mL (0.96
mmol, 1.2 equiv) of tetrabutylammonium fluoride (1.0 M
solution in THF). The reaction mixture was stirred at 22 °C
for 3 h, diluted with EtOAc, washed with brine, dried (Na2-
SO4), and purified by chromatography on SiO2 (EtOAc/hex-
anes, 1:4) to give 170 mg (89%) of (4E,6E,10R)-10-methoxy-
7-methyltrideca-4,6,12-trien-1-ol as a colorless oil: [R]D -1.8°
(4E,6E)-10-[(ter t-Bu tyldiph en ylsilyl)oxy]-4-m eth yldeca-
4,6-d ien a l (14). A solution of 1.0 g (2.56 mmol) of 11 in 10
mL of THF was treated at 22 °C with 0.66 g (2.56 mmol, 1.0
equiv) of Cp2Zr(H)Cl. The reaction mixture was stirred at 40
°C overnight. Butyl isocyanide (0.29 mL, 2.81 mmol) was
added dropwise at 0 °C, and the solution was stirred at 22 °C
for 4 h. After addition of Et2O (10 mL), the solution was cooled
to -78 °C, and 3 M HCl (2 mL) was added with vigorous
stirring. The reaction mixture was warmed to 0 °C, and the
organic layer was separated, washed with saturated aqueous
NaHCO3 solution and brine, and dried (Na2SO4). The solvent
was removed, and the product was purified by chromatography
on Florisil (EtOAc/hexanes, 1:30) to give 0.58 g (54%) of 14 as
(c 1.0, CHCl3); IR (neat) 3392, 1095, 1060 cm-1 1H NMR δ
;
6.26 (dd, 1 H, J ) 15.0, 10.7 Hz), 5.84-5.73 (m, 2 H), 5.57 (dt,
1 H, J ) 15.0, 7.0 Hz), 5.10-5.03 (m, 2 H), 3.65 (t, 2 H, J )
6.4 Hz), 3.33 (s, 3 H), 3.17 (p, 1 H, J ) 5.8 Hz), 2.28-2.00 (m,
6 H), 1.78 (s, 3 H), 1.68-1.55 (m, 5 H); 13C NMR δ 136.7, 134.8,
131.5, 127.3, 124.7, 117.1, 80.0, 62.5, 56.6, 37.7, 35.4, 32.5, 31.6,
29.3, 16.6; MS (EI) m/z (relative intensity) 238 (M+); HRMS
(EI) m/z calcd for C15H26O2 238.1933, found 238.1944.
Met h a n esu lfon ic Acid (4E,6E,10R)-10-Met h oxy-7-
m eth yltr id eca -4,6,12-tr ien yl Ester . To a solution of 120 mg
(0.50 mmol) of (4E,6E,10R)-10-methoxy-7-methyltrideca-4,6,-
12-trien-1-ol in 1 mL of CH2Cl2 was added triethylamine (84
µL, 0.6 mmol) followed by methanesulfonyl chloride (42 µL,
0.55 mmol). The reaction mixture was stirred at 22 °C
overnight and concentrated in vacuo, and the residue was
purified by chromatography on SiO2 (EtOAc/hexanes, 1:4) to
give 150 mg (95%) of methanesulfonic acid (4E,6E,10R)-10-
methoxy-7-methyltrideca-4,6,12-trienyl ester as a colorless
oil: [R]D -1.0° (c 0.9, CHCl3); IR (neat) 1356, 1176, 1094, 966
1
a colorless oil: IR (neat) 1724, 1111, 822, 701 cm-1; H NMR
δ 9.78 (t, 1 H, J ) 1.6 Hz), 7.69-7.66 (m, 4 H), 7.45-7.35 (m,
6 H), 6.23 (dd, 1 H, J ) 15.0, 10.8 Hz), 5.80 (d, 1 H, J ) 10.6
Hz), 5.59 (dt, 1 H, J ) 15.0, 7.1 Hz), 3.68 (t, 2 H, J ) 6.3 Hz),
2.56 (t, 2 H, J ) 7.5 Hz), 2.38 (t, 2 H, J ) 7.5 Hz), 2.22 (q, 2
H, J ) 7.3 Hz), 1.74 (s, 3 H), 1.64 (p, 2 H, J ) 6.7 Hz), 1.05 (s,
9 H); 13C NMR δ 202.3, 135.6, 134.1, 133.8, 133.1, 129.6, 127.7,
126.6, 125.7, 63.3, 42.1, 32.4, 32.0, 29.3, 26.9, 19.3, 16.7; MS
(EI) m/z (relative intensity) 363 ([M - C4H9]+); HRMS (EI) m/z
calcd for C23H27O2Si (M - C4H9) 363.1780, found 363.1776.
1
cm-1; H NMR δ 6.26 (dd, 1 H, J ) 15.0, 10.9 Hz), 5.82-5.73
(m, 2 H), 5.48 (dt, 1 H, J ) 15.0, 7.0 Hz), 5.08-5.01 (m, 2 H),
4.20 (t, 2 H, J ) 6.4 Hz), 3.31 (s, 3 H), 3.20-3.13 (m, 1 H),
2.97 (s, 3 H), 2.26-1.97 (m, 6 H), 1.82 (p, 2 H, J ) 6.9 Hz),
1.70 (s, 3 H), 1.61-1.52 (m, 2 H); 13C NMR δ 137.4, 134.7,
129.4, 128.2, 124.3, 117.0, 79.8, 69.4, 56.5, 37.6, 37.3, 35.3, 31.6,
28.9, 28.6, 16.6; MS (EI) m/z (relative intensity) 316 (M+);
HRMS (EI) m/z calcd for C16H28O4S 316.1708, found 316.1694.
(4R,7E,9E)-13-Iod o-4-m et h oxy-7-m et h ylt r id eca -1,7,9-
tr ien e. To a solution of 56 mg (0.17 mmol) of methanesulfonic
acid (4E,6E,10R)-10-methoxy-7-methyltrideca-4,6,12-trienyl
ester in 1 mL of acetone was added 80 mg (0.51 mmol, 3.0
equiv) of NaI. The reaction mixture was heated at reflux for
2 h, and acetone was removed in vacuo. The residue was
diluted with CH2Cl2 (2 mL) and water (1 mL). The aqueous
layer was extracted with CH2Cl2 (3×), and the combined
organic layers were dried (Na2SO4) and concentrated in vacuo.
The residue was purified by chromatography on SiO2 (EtOAc/
hexanes, 1:20) to give 59 mg (99%) of (4R,7E,9E)-13-iodo-4-
methoxy-7-methyltrideca-1,7,9-triene as a colorless oil: [R]D
-1.5° (c 1.0, CHCl3); IR (neat) 1440, 1096, 964 cm-1; 1H NMR
δ 6.28 (dd, 1 H, J ) 15.0, 10.9 Hz), 5.84-5.73 (m, 2 H), 5.48
(dt, 1 H, J ) 15.0, 7.0 Hz), 5.09-5.04 (m, 2 H), 3.33 (s, 3 H),
3.27-3.15 (m, 3 H), 2.28-2.01 (m, 6 H), 1.94-1.87 (m, 2 H),
1.72 (s, 3 H), 1.62-1.49 (m, 2 H); 13C NMR δ 137.1, 134.8,
129.5, 128.2, 124.5, 117.0, 79.9, 56.6, 37.7, 35.4, 33.5, 33.1, 31.6,
16.6, 6.6; MS (EI) m/z (relative intensity) 348 (M+); HRMS (EI)
m/z calcd for C15H25OI 348.0950, found 348.0929.
(4R,7E,9E)-13-[(ter t-Bu tyld ip h en ylsilyl)oxy]-7-m eth yl-
tr id eca -1,7,9-tr ien -4-ol (13). A solution of (-)-B-methoxy-
diisopinocampheylborane (300 mg, 0.95 mmol) in 1.0 mL of
dry Et2O was cooled to 0 °C, and allylmagnesium bromide (0.95
mL, 0.95 mmol) (1.0 M solution in Et2O) was added dropwise.
The reaction mixture was vigorously stirred at 22 °C for 1 h
and cooled to -78 °C, and a solution of 14 (400 mg, 0.95 mmol)
in 1.0 mL of Et2O was added dropwise. The mixture was
stirred at -78 °C for 4 h, 60 µL (0.95 mmol) of ethanolamine
was added, and stirring was continued at 22 °C for 2 h. After
addition of Et2O, the organic layer was washed with brine,
dried (Na2SO4), and chromatographed on SiO2 (EtOAc/hex-
anes, 1:10) to give 277 mg (63%) of 13 as a colorless oil: [R]D
-7.2° (c 0.6, CHCl3); IR (neat) 3360, 1111, 702 cm-1; 1H NMR
δ 7.69-7.66 (m, 4 H), 7.45-7.35 (m, 6 H), 6.24 (dd, 1 H, J )
15.0, 10.8 Hz), 5.85-5.79 (m, 2 H), 5.56 (dt, 1 H, J ) 15.0, 7.0
Hz), 5.17-5.12 (m, 2 H), 3.67 (t, 2 H, J ) 6.4 Hz), 3.69-3.65
(m, 1 H), 2.31-2.05 (m, 6 H), 1.74 (s, 3 H), 1.70-1.58 (m, 5
H), 1.05 (s, 9 H); 13C NMR δ 136.0, 135.6, 134.8, 134.1, 132.3,
129.6, 127.7, 126.9, 125.1, 118.3, 70.5, 63.3, 42.0, 36.0, 34.9,
32.5, 29.2, 26.9, 19.3, 16.6; MS (EI) m/z (relative intensity) 462
(M+); HRMS (EI) m/z calcd for C30H42O2Si 462.2954, found
462.2965.
ter t-Bu tyl-(4E,6E,10R)-[(10-m eth oxy-7-m eth yltr id eca -
4,6,12-tr ien yl)oxy]d ip h en ylsila n e. To a suspension of NaH
(83 mg, 60%, 2.08 mmol) in 1.0 mL of THF was added dropwise
480 mg (1.04 mmol) of 13 in 2 mL of THF. The mixture was
stirred at 22 °C for 2 h, treated dropwise with 0.13 mL (2.08
mmol) of methyl iodide, and stirred at 22 °C for 4 h. Water
was added slowly, and the reaction mixture was extracted with
Et2O (3×). The combined ether layers were dried (Na2SO4)
and purified by chromatography on SiO2 (EtOAc/hexanes, 1:30)
to give 445 mg (90%) of tert-butyl-(4E,6E,10R)-[(10-methoxy-
7-methyltrideca-4,6,12-trienyl)oxy]diphenylsilane as a colorless
oil: [R]D -1.1° (c 0.35, CHCl3); IR (neat) 1111, 1095, 823, 702
cm-1; 1H NMR δ 7.69-7.66 (m, 4 H), 7.45-7.34 (m, 6 H), 6.25
(dd, 1 H, J ) 15.0, 10.7 Hz), 5.86-5.77 (m, 2 H), 5.56 (dt, 1 H,
J ) 15.0, 6.9 Hz), 5.12-5.05 (m, 2 H), 3.67 (t, 2 H, J ) 6.4
Hz), 3.35 (s, 3 H), 3.17 (p, 1 H, J ) 5.9 Hz), 2.31-2.03 (m, 6
H), 1.73 (s, 3 H), 1.68-1.56 (m, 4 H), 1.05 (s, 9 H); 13C NMR δ
136.3, 135.7, 134.8, 134.1, 132.0, 129.6, 127.7, 127.0, 124.9,
117.1, 80.0, 63.3, 56.7, 37.7, 35.4, 32.5, 31.7, 29.3, 26.9, 19.3,
[(4R,7E,9E)-4-Meth oxy-7-m eth yltr id eca -1,7,9-tr ien -13-
yl]tr ip h en ylp h osp h on iu m Iod id e (16). A solution of 120
mg (0.35 mmol) of (4R,7E,9E)-13-iodo-4-methoxy-7-methyl-
trideca-1,7,9-triene and 90 mg (0.35 mmol) of triphenylphos-
phine in 2 mL of degassed acetonitrile was transferred into
an ampule, sealed, and heated at 90 °C for 24 h. The reaction
mixture was concentrated in vacuo, and the residue (220 mg,
quantitative) was used without further purification: 1H NMR
δ 7.78-7.65 (m, 15 H), 6.24 (dd, 1 H, J ) 15.0, 10.9 Hz), 5.77-
5.68 (m, 2 H), 5.36 (dt, 1 H, J ) 14.9, 7.3 Hz), 5.02-4.96 (m,
2 H), 3.62-3.52 (m, 2 H), 3.27 (s, 3 H), 3.14-3.10 (m, 1 H),
2.45-1.96 (m, 6 H), 1.66 (s, 3 H), 1.66-1.18 (m, 4 H).
(1R,2S)-2-Meth ylcyclop r op a n eca r boxylic Acid (18). To
a solution of 1.8 g (21.0 mmol) of alcohol 17 and 18.0 g (84
mmol) of NaIO4 in 42 mL of CCl4, 42 mL of CH3CN, and 63
mL of H2O was added 130 mg (0.63 mmol) of RuCl3‚H2O. The
reaction mixture was vigorously stirred at 22 °C for 6 h, Et2O