6658 J . Org. Chem., Vol. 65, No. 20, 2000
Mukai et al.
24.87; MS m/z 194 (M+, 0.5). Anal. Calcd for C12H18O2: C,
74.19; H, 9.34. Found: C, 74.36; H, 9.62.
-4.83; MS m/z 396 (M+, 17.8). Anal. Calcd for C22H44O2Si2:
C, 66.60; H, 11.18. Found: C, 66.95; H, 11.46.
(6S,7S)-6,7-(Isop r op ylid en ed ioxy)-9-p h en yln on -1-en -8-
yn e ((-)-6b). To a solution of 6a (450 mg, 2.32 mmol) in THF
(23 mL) was successively added CuI (26.5 mg, 0.14 mmol),
iodobenzene (0.57 mL, 2.78 mmol), and Pd(PPh3)2Cl2 (48.8 mg,
(6S ,7S )-Bis(t er t -b u t yld im e t h ylsiloxy)u n d e c-1-e n -8-
yn e ((-)-8c). According to the procedure described for conver-
sion of 6a to 8b, the title compound (-)-8c (751 mg, 71%) was
obtained from 6a (500 mg, 2.57 mmol). Compound (-)-8c was
a colorless: [R]24D -9.5 (c 1.00, CHCl3); IR 1639 cm-1; 1H NMR
δ 5.82 (ddt, 1H, J ) 17.1, 10.3, 6.8 Hz), 5.00 (dd, 1H, J ) 17.1,
3.4 Hz), 4.93 (m, 1H), 4.30 (dt, 1H, J ) 5.4, 2.0 Hz), 3.56 (ddd,
1H, J ) 7.4, 5.4, 3.9 Hz), 2.20 (qd, 2H, J ) 7.6, 2.0 Hz), 2.08-
2.03 (m, 2H), 1.75-1.35 (m, 4H), 1.12 (t, 3H, J ) 7.6 Hz), 0.90
(s, 9H), 0.90 (s, 9H), 0.12 (s, 3H), 0.09 (s, 3H), 0.06 (s, 3H),
0.06 (s, 3H); 13C NMR δ 139.07, 114.18, 86.96, 78.76, 77.47,
74.99, 67.19, 65.84, 33.89, 31.52, 25.88, 25.68, 24.67, 18.28,
18.10, 15.26, 13.77, 12.46, -4.35, -4.53, -4.78; MS m/z 410
(M+, 8.9). Anal. Calcd for C23H46O2Si2: C, 67.25; H, 11.29.
Found: C, 67.39; H, 11.23.
i
0.07 mmol). After stirring for 5 min at room temperature, -
Pr2NH (3.30 mL, 23.2 mmol) was added to the reaction
mixture, which was further stirred for 2h. The resulting
precipitates were filtered off and the filtrate was concentrated
to leave a residual oil, which was chromatographed with
hexane-AcOEt (50:1) to afford (-)-6b (548 mg, 87%) as a
colorless oil: [R]23D -43.8 (c 1.00, CHCl3); IR 2232, 1640 cm-1
;
1H NMR δ 7.47-7.43 (m, 2H), 7.33-7.29 (m, 3H), 5.82 (ddt,
1H, J ) 17.1, 10.3, 6.8 Hz), 5.03 (dd, 1H, J ) 17.1, 3.4 Hz),
4.97 (m, 1H), 4.45 (d, 1H, J ) 7.8), 4.11 (dt, 1H, J ) 7.8, 5.6
Hz), 2.17-2.11 (m, 2H), 1.75-1.55 (m, 4H), 1.51 (s, 3H), 1.45
(s, 3H); 13C NMR δ 138.26, 131.79, 128.59, 128.25, 122.32,
114.90, 109.69, 86.42, 85.66, 81.47, 71.05, 33.61, 31.79, 27.17,
26.31, 24.94; MS m/z 270 (M+, 3.7). Anal. Calcd for C18H22O2:
C, 79.96; H, 8.20. Found: C, 79.82; H, 8.49.
(6S,7S)-Bis(ter t-b u t yld im et h ylsiloxy)n on -1-en -8-yn e
((-)-8d ). According to the procedure described for conversion
of 6a to 8b, the title compound (-)-8d (127 mg, 80%) was
obtained from 6a (80.7 mg, 0.42 mmol). Compound (-)-8d was
(3S,4S)-1-P h en yln on -8-en -1-yn e-3,4-d iol ((-)-7). A solu-
tion of 6b (548 mg, 2.03 mmol) in MeOH (20 mL) containing
10 drops of 10% HCl solution was heated at reflux for 1 h.
MeOH was evaporated off, and the residue was taken up in
CHCl3 which was washed with water, dried, and concentrated
to dryness. Chromatography of the residue with hexane-
AcOEt (2:1) afforded (-)-7 (423 mg, 92%) as a colorless oil:
a colorless oil: [R]23D -15.7 (c 1.00, CHCl3); IR 3307, 1639 cm-1
;
1H NMR δ 5.82 (ddt, 1H, J ) 17.1, 10.3, 6.8 Hz), 5.01 (dd, 1H,
J ) 17.1, 3.4 Hz), 4.94 (m, 1H), 4.33 (dd, 1H, J ) 4.8, 2.4 Hz),
3.57 (ddd, 1H, J ) 7.8, 4.8, 3.4 Hz), 2.32 (d, 1H, J ) 2.4 Hz),
2.09-2.04 (m, 2H), 1.77-1.37 (m, 4H), 0.90 (s, 9H), 0.90 (s,
9H), 0.13 (s, 3H), 0.09 (s, 3H), 0.06 (s, 3H), 0.06 (s, 3H); 13C
NMR δ 138.94, 114.30, 83.16, 74.52, 73.16, 66.92, 33.82, 31.20,
25.84, 25.77, 24.84, 18.17, 18.08, -4.42, -4.54, -4.65, -4.96;
MS m/z 382 (M+, 17.8). Anal. Calcd for C21H42O2Si2: C, 65.73;
H, 11.06. Found: C, 65.73; H, 11.37.
[R]24 -24.2 (c 1.00, CHCl3); IR 3567, 3413, 2228, 1640 cm-1
;
D
1H NMR δ 7.45-7.42 (m, 2H), 7.35-7.28 (m, 3H), 5.81 (ddt,
1H, J ) 17.1, 10.3, 6.8 Hz), 5.02 (dd, 1H, J ) 17.1, 3.4 Hz),
4.96 (m, 1H), 4.39 (d, 1H, J ) 6.8), 3.74 (m, 1H), 2.74 (brs,
2H), 2.15-2.04 (m, 2H), 1.81-1.48 (m, 4H); 13C NMR δ 13845,
131.72, 128.55, 128.23, 122.14, 114.68, 87.78, 86.36, 74.68,
66.52, 33.50, 32.29, 24.76; MS m/z 230 (M+, 1.8). Anal. Calcd
for C15H18O2: C, 78.23; H, 7.88. Found: C, 77.86; H, 7.97.
Gen er a l P r oced u r e for P a u son -Kh a n d R ea ct ion of
Eyn yn e. Con d ition B. Co2(CO)8 (0.24 mmol) was added to a
solution of enyne (0.20 mmol) in Et2O (2.0 mL) at room
temperature. The reaction mixture was stirred for 1 h and
concentrated to leave the residue. The crude cobalt-complexed
enyne was dissolved in THF (5.0 mL), to which TMANO‚2H2O
(1.2 mmol) was added at 0 °C. The reaction mixture was stirred
at room temperature until disappearance of the starting
material. The reaction mixture was concentrated and the
residue was purified by silica gel chromatography with hexane-
AcOEt to give cyclized products. Con d ition C. A solution of
the crude cobalt-complexed enyne and CyNH2 (0.80 mmol) in
1,2-dichloroethane (2.0 mL) was heated at reflux for 15 min.
Workup and chromatography provided cyclized products.
Con d ition D. A solution of the crude cobalt-complexed enyne
and MeSPh (0.7 mmol) in 1,2-dichloroethane (2.0 mL) was
heated at reflux for 1 h. Workup and chromatography provided
cyclized products. Con d ition E. A solution of the crude cobalt-
complexed enyne and MeSPri (2.00 mmol) in 1,2-dichloroet-
hane (2.0 mL) was heated at reflux for 1 h. Workup and
chromatography provided cyclized products. Con d ition F . A
solution of the crude cobalt-complexed enyne and MeSBun
(0.70 mmol) in 1,2-dichloroethane (2.0 mL) was heated at
reflux for 15 min. Workup and chromatography provided
cyclized products. Chemical yields and ratio between 9 and
10 are summarized in Table 1.
(2S,3S,6S,7S)- a n d (2S,3S,6S,7R)-Bis(ter t-bu tyld im eth -
ylsiloxy)-7-m et h yl-9-p h en ylb icyclo[4.3.0]n on -1(9)-en -8-
on es (9a a n d 10a ). A mixture of 9a and 10a was obtained in
a ratio of 93:7 (entry 4 in Table 1). The ratio was determined
by HPLC analysis (hexane-AcOEt)50:1; 1.0 mL/min; retention
time of 9a was recorded as 7.9 min and that of 10a as 9.1 min).
A mixture of 9a and 10a was a colorless oil: IR 1695, 1646
cm-1; 1H NMR δ 7.75-7.24 (m, 5H), 4.93 (d, 93/100 × 1H, J )
3.4 Hz), 4.91 (d, 7/100 × 1H, J ) 3.9 Hz), 4.09 (m, 1H), 2.99
(m, 7/100 × 1H), 2.60 (m, 93/100 × 1H), 2.33 (m, 7/100 × 1H),
2.10 (m, 1H), 1.88 (dq, 93/100 × 1H, J ) 7.3, 2.9 Hz), 1.70 (m,
1H), 1.60-1.51 (m, 2H), 1.21 (d, 93/100 × 3H, J ) 7.3 Hz),
1.03 (d, 7/100 × 3H, J ) 4.9 Hz), 0.91 (s, 93/100 × 9H), 0.87
(s, 7/100 × 9H), 0.86 (s, 7/100 × 9H), 0.83 (s, 93/100 × 9H),
0.06 (s, 93/100 × 3H), 0.02 (s, 7/100 × 3H), 0.00 (s, 93/100 ×
3H), -0.02 (s, 7/100 × 3H), -0.13 (s, 7/100 × 3H), -0.14 (s,
7/100 × 3H), -0.19 (s, 93/100 × 3H), -0.21 (s, 93/100 × 3H);
(6S,7S)-Bis(ter t-b u t yld im et h ylsiloxy)-9-p h en yln on -1-
en -8-yn e ((-)-8a ). To a solution of 7 (250 mg, 1.09 mmol) and
imidazole (443 mg, 6.51 mmol) in DMF (1.0 mL) was added
TBDMSCl (491 mg, 3.26 mmol) at room temperature. The
reaction mixture was stirred at the same temperature for 1 h,
quenched by addition of water, and extracted with Et2O. The
extract was washed with water and brine, dried, and concen-
trated to dryness. Chromatography of the residue with hexane
afforded (-)-8a (474 mg, 95%) as a colorless oil: [R]23 -11.5
D
(c 1.00, CHCl3); IR 1639 cm-1; H NMR δ 7.43-7.27 (m, 5H),
1
5.83 (ddt, 1H, J ) 17.1, 10.3, 6.8 Hz), 5.04 (dd, 1H, J ) 17.1,
1.5 Hz), 4.96 (m, 1H), 4.55 (d, 1H, J ) 5.3), 3.68 (ddd, 1H, J )
8.2, 5.3, 3.4 Hz), 2.11-2.05 (m, 2H), 1.84-1.45 (m, 4H), 0.93
(s, 9H), 0.92 (s, 9H), 0.18 (s, 3H), 0.14 (s, 3H), 0.10 (s, 3H),
0.08 (s, 3H); 13C NMR δ 138.99, 131.48, 128.18, 127.96, 123.38,
114.30, 89.08, 85.16, 74.95, 67.55, 33.89, 31.68, 25.88, 24.75,
18.30, 18.10, -4.33, -4.45, -4.49, -4.74; MS m/z 458 (M+,
13.5). Anal. Calcd for C27H46O2Si2: C, 70.68; H, 10.11. Found:
C, 70.45; H, 10.40.
(6S,7S)-Bis(ter t-bu tyldim eth ylsiloxy)dec-1-en -8-yn e ((-
)-8b).To a solution of 6a (333 mg, 1.72 mmol) in THF (17 mL)
was added n-BuLi (1.41 M hexane solution, 1.38 mL, 2.56
mmol) at -50 °C. After stirring for 30 min at the same
temperature, MeI (1.07 mL, 17.2 mL) was added to the
reaction mxiture, which was then stirred at room-temperature
overnight. The mixture was quenched by addition of saturated
aqueous NH4Cl, extracted with Et2O. The extract was washed
with water and brine, dried, and concentrated to give the crude
product, which was successively hydrolyzed and silylated,
according to the procedure described for conversion of 6b to
8a , to afford (-)-8b (479 mg, 72%) as a colorless oil: [R]23
D
-13.2 (c 1.00, CHCl3); IR 1639 cm-1; 1H NMR δ 5.83 (ddt, 1H,
J ) 17.1, 10.3, 6.6 Hz), 5.00 (dd, 1H, J ) 17.1, 3.6 Hz), 4.94
(m, 1H), 4.29 (m, 1H), 3.55 (ddd, 1H, J ) 8.9, 5.3, 3.1 Hz),
2.07-2.06 (m, 2H), 1.82 (s, 3H), 1.73-1.35 (m, 4H), 0.90 (s,
9H), 0.90 (s, 9H), 0.12 (s, 3H), 0.09 (s, 3H), 0.06 (s, 3H), 0.06
(s, 3H); 13C NMR δ 139.07, 114.20, 81.10, 78.51, 75.02, 67.23,
33.89, 31.48, 25.88, 24.78, 18.28, 18.13, 3.61, -4.35, -4.51,