D. Sawada et al. / Tetrahedron 66 (2010) 5407e5423
5413
1H), 2.41e2.44 (m, 2H), 3.56 (m, 2H), 4.01 (dt, J¼6.1, 3.4 Hz, 1H),
(400 MHz, CDCl3)
d
0.00 (s, 9H), 0.04 (s, 3H), 0.877 (s, 9H), 0.884 (s,
4.10 (dd, J¼6.7, 5.7 Hz, 1H), 4.22 (dt, J¼6.1, 2.1 Hz, 2H), 5.08 (dd,
J¼10.1, 1.0 Hz, 1H), 5.13 (dd, J¼17.2, 1.0 Hz, 1H), 5.83 (ddd, J¼17.2,
9H), 1.32 (t, J¼6.0 Hz, 1H), 2.18e2.25 (m, 2H), 2.33 (dd, J¼16.8,
6.4 Hz, 1H), 2.60 (dd, J¼14.3, 5.5 Hz, 1H), 2.66 (dd, J¼14.3, 7.1 Hz,
1H), 4.02 (ddd, J¼6.5, 6.4, 2.4 Hz, 1H), 4.14e4.19 (m, 3H), 5.06 (d,
J¼10.0 Hz, 1H), 5.14 (d, J¼17.2 Hz, 1H), 5.18 (ddd, J¼17.2, 10.0, 7.5 Hz,
10.1, 6.7 Hz, 1H); 13C NMR (100 MHz, CDCl3)
d
ꢁ5.2, ꢁ5.2, ꢁ4.6,
ꢁ4.3, ꢁ4.1, ꢁ3.5, 18.1, 18.2, 18.4, 22.2, 25.9 (3C), 26.0 (3C), 26.5 (3C),
32.5, 49.4, 51.3, 63.6, 71.5, 76.1, 80.0, 84.0, 115.4, 140.3; EI-LRMS m/z
553 (M-OH)þ, 513, 438, 381, 369, 171; EI-HRMS calcd for
C30H61O3Si3 (MꢁOH)þ 553.3928, found 553.3928.
1H), 7.11e7.24 (m, 5H); 13C NMR (100 MHz, CDCl3)
d
ꢁ4.6, ꢁ4.4,
ꢁ4.1, ꢁ3.5, 18.2, 18.3, 26.0 (3C), 26.0 (3C), 26.1, 32.1, 51.4, 51.6, 71.0,
75.9, 79.8, 84.3, 115.7, 125.5, 128.0 (2C), 129.2 (2C), 140.4, 142.1; EI-
LRMS m/z 431 (Mꢁ Bu)þ, 339, 287, 207; EI-HRMS calcd for
t
t
4.2.3. (5R,6S,7R)-5,7-Bis(tert-butyldimethylsilanyloxy)-6-[3-(tert-
butyldimethylsilanyloxy)propoxy]-non-8-en-2-yn-1-ol (8c). In the
same procedure for 8a, 8c (2.07 g, 89%) was obtained from 4c2
(2.31 g, 4.15 mmol), nBuLi (1.53 M hexane solution, 3.9 mL,
5.97 mmol), paraformaldehyde (424 mg, 14.1 mmol), and THF
C24H39O3Si2 (Mꢁ Bu)þ 431.2438, found 431.2455.
4.2.7. (2Z)-(5R,6S,7R)-5,7-Bis(tert-butyldimethylsilanyloxy)-3-iodo-
6-methylnona-2,8-dien-1-ol (9a). To
a solution of 8a (1.00 g,
2.43 mmol) in dry Et2O (25 mL) was added Red-AlÒ (65% toluene
solution, 1.73 mL, 5.76 mmol) at 0 ꢀC and stirred at room temper-
ature for 4 h. To the mixture was added ethyl acetate (0.41 mL,
4.20 mmol) at 0 ꢀC, and then cooled to ꢁ78 ꢀC and added I2 (1.28 g,
5.03 mmol) in THF (2 mL) and stirred at the same temperature for
30 min. The mixture was warmed up to room temperature over
1.5 h and stirred for 10 min. The mixture was diluted with Et2O,
added 10% Na2S2O3 aqueous solution and saturated NaHCO3
aqueous solution at 0 ꢀC, and the aqueous layer was extracted with
Et2O. The organic layer was washed with brine, dried over Na2SO4,
and concentrated. The residue was purified by flash column chro-
(13.1 mL). Colorless oil; [
a
]
25 þ0.42 (c 2.62, CHCl3); IR (neat) 3443,
D
2290,1644,1252 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d
0.03 (s, 3H), 0.05
(s, 3H), 0.06 (s, 3H), 0.08 (s, 3H), 0.10 (s, 3H), 0.88 (s, 9H), 0.89 (s, 9H),
0.90 (s, 9H),1.54 (t, J¼6.1 Hz,1H),1.71e1.82 (m, 2H), 2.38 (ddt, J¼18.8,
6.4, 5.4 Hz, 1H), 2.53 (ddt, J¼16.8, 6.8, 5.7 Hz, 1H), 3.33 (dd, J¼5.5,
3.3 Hz, 1H), 3.59e3.76 (m, 4H), 3.84 (dt, J¼5.7, 5.5 Hz, 1H), 4.23 (m,
2H), 4.30 (m,1H), 5.12 (ddd, J¼10.3,1.7,1.0 Hz,1H), 5.22 (ddd, J¼17.3,
1.7, 1.2 Hz, 1H), 5.95 (ddd, J¼17.3, 10.3, 6.9 Hz, 1H); 13C NMR
(100 MHz, CDCl3)
d
ꢁ5.2 (2C), ꢁ4.7, ꢁ4.3, ꢁ4.1, ꢁ4.0, 18.2, 18.3, 18.4,
24.4, 25.9, 27.0, 26.0, 33.5, 51.4, 60.6, 69.3, 71.8, 74.5, 79.8, 84.2, 85.1,
115.9, 138.7; EI-LRMS m/z 569 (M-OH)þ, 529, 415, 339, 327, 115; EI-
HRMS calcd for C30H61O4Si3 (MꢁOH)þ 569.3898, found 569.3888.
matography on silica gel (hexane/AcOEt¼10/1) to give 9a (985 mg,
24
62%) as a colorless oil: [
a
]
þ1.22 (c 2.38, CHCl3); IR (neat) 3328,
D
1644,1252, 675 cmꢁ1; 1H NMR (400 MHz, CDCl3)
d 0.03 (s, 3H), 0.06
4.2.4. (5R,6S,7R)-5,7-Bis(tert-butyldimethylsilanyloxy)-6-butylnon-
8-en-2-yn-1-ol (8d). In the same procedure for 8a, 8d (1.03 g, 91%)
was obtained from 4d23d (1.135 g, 2.50 mmol), nBuLi (1.57 M hexane
(s, 3H), 0.08 (s, 3H), 0.10 (s, 3H), 0.73 (d, J¼7.2 Hz, 3H), 0.88 (s, 9H),
0.89 (s, 9H), 1.51 (br s, 1H), 1.57 (ddq, J¼7.3, 7.2, 2.0 Hz, 1H),
2.69e2.70 (m, 2H), 3.98 (dd, J¼7.8, 7.3 Hz, 1H), 4.20 (d, J¼5.6 Hz,
2H), 4.32 (dt, J¼6.6, 2.0 Hz, 1H), 5.08e5.13 (m, 2H), 5.71 (ddd,
J¼17.8, 9.6, 7.8 Hz, 1H), 5.88 (t, J¼5.6 Hz, 1H); 13C NMR (100 MHz,
solution, 2.4 mL, 3.77 mmol), paraformaldehyde (226 mg,
20
7.52 mmol), and THF (8.3 mL). Colorless oil; [
a
]
D
þ1.46 (c 2.54,
CHCl3); IR (neat) 3347, 2957, 2228, 1253, 1074 cmꢁ1
;
1H NMR
CDCl3)
d
ꢁ4.3, ꢁ4.0, ꢁ3.4, ꢁ3.0, 9.5 (2C), 18.3, 18.3, 26.0 (3C), 26.2
(400 MHz, CDCl3) 0.00 (s, 3H), 0.03 (s, 3H), 0.04 (s, 3H), 0.07 (s,
d
(3C), 42.9, 50.9, 67.3, 70.1, 76.4, 116.0, 135.7, 140.7; EI-LRMS m/z 483
t
3H), 0.84e0.87 (m, 2H), 0.87 (s, 9H), 0.87 (s, 9H), 1.22e1.32 (m, 6H),
1.37 (dt, J¼6.0, 0.9 Hz, 1H), 1.68 (dd, J¼5.2, 3.8 Hz, 1H), 2.40e2.42
(m, 2H), 3.95 (ddd, J¼6.2, 6.2, 3.7 Hz, 1H), 4.10 (dd, J¼7.2, 6.5 Hz,
1H), 4.21 (dd, J¼2.0, 2.0 Hz, 1H), 4.22 (dd, J¼2.0, 2.0 Hz, 1H), 5.04
(dd, J¼10.1, 1.1 Hz, 1H), 5.83 (ddd, J¼17.3, 10.1, 7.2 Hz, 1H); 13C NMR
(Mꢁ Bu)þ, 415, 355, 241, 115; EI-HRMS calcd for C18H36IO3Si2
t
(Mꢁ Bu)þ 483.1248, found 483.1247.
4.2.8. (2Z)-(5R,6S,7R)-5,7-Bis(tert-butyldimethylsilanyloxy)-6-[3-
(tert-butyldimethylsilanyloxy)propyl]-3-iodonona-2,8-dien-1-ol
(9b). In the same procedure for 9a, 9b (1.01 g, 70%) was obtained
from 8b (1.19 g, 2.08 mmol), Red-AlÒ (65% toluene solution,
(100 MHz, CDCl3)
d
ꢁ4.6, ꢁ4.3, ꢁ4.1, ꢁ3.6, 14.1, 18.1, 23.2, 25.9 (3C),
25.9 (3C), 26.3, 31.5, 49.6, 51.4, 71.8, 75.8, 79.7, 84.4, 115.1, 140.4; EI-
LRMS m/z 397 (Mꢁ Bu)þ, 265, 131, 115; EI-HRMS calcd for
1.75 mL, 5.83 mmol), ethyl acetate (0.32 mL, 3.28 mmol), Et2O
t
t
25
C21H41O3Si2 (Mꢁ Bu)þ 397.2495, found 397.2582.
(25 mL), I2 (1.27 g, 4.99 mmol), and THF (2 mL). Colorless oil; [a]
D
þ1.89 (c 2.54, CHCl3); IR (neat) 3320,1644,1254, 671 cmꢁ1; 1H NMR
4.2.5. (5R,6S,7R)-5,7-Bis(tert-butyldimethylsilanyloxy)-6-phenylnon-
8-en-2-yn-1-ol (8e). In the same procedure for 8a, 8e (360 mg, 81
%) was obtained from 4e23e (470 mg, 1.0 mmol), nBuLi (1.56 M
(400 MHz, CDCl3) d 0.01 (s, 3H), 0.04 (s, 12H), 0.07 (s, 3H), 0.87 (s,
9H), 0.88 (s, 9H), 0.89 (s, 9H), 1.29e1.31 (m, 2H), 1.56e1.64 (m, 4H),
2.70 (dd, J¼7.2, 6.2 Hz, 2H), 3.57 (t, J¼6.4 Hz, 2H), 4.12e4.23 (m,
4H), 5.06 (dd, J¼10.3,1.2 Hz,1H), 5.13 (dd, J¼17.2,1.2 Hz,1H), 5.86 (t,
hexane solution 1.0 mL, 1.56 mmol), paraformaldehyde (95 mg,
21
3.1 mmol), and THF (3 mL). White amorphous solid; [
0.01, CHCl3); IR (neat) 3346, 1253, 1217 cmꢁ1
CDCl3) 0.04 (s, 3H), 0.06 (s, 3H), 0.10 (s, 6H), 0.86 (s, 9H), 0.92 (s,
a
]
ꢁ37.3 (c
J¼6.2 Hz, 1H), 5.88 (m, 1H); 13C NMR (100 MHz, CDCl3)
d
ꢁ5.1 (2C),
D
;
1H NMR (400 MHz,
ꢁ4.5, ꢁ3.9, ꢁ3.6, ꢁ3.4,18.2,18.2,18.4,18.4, 22.4, 26.0 (3C), 26.1 (6C),
d
32.3, 49.5, 50.8, 63.5, 67.4, 71.4, 75.9, 107.6, 115.4, 136.1, 140.7; EI-
t
9H), 1.33 (s, 1H), 2.03 (ddd, J¼16.4, 9.5, 2.0 Hz, 1H), 2.28 (dt, J¼16.4,
2.2 Hz, 1H), 2.97 (dd, J¼2.4, 9.0 Hz, 1H), 4.27 (s, 2H), 4.47e4.53 (m,
2H), 4.86 (dd, J¼1.2, 10.3 Hz, 1H), 4.92 (dd, J¼17.1, 1.2 Hz, 1H), 5.53
(ddd, J¼17.1, 10.3, 8.8 Hz, 1H), 7.14e7.21 (m, 5H); 13C NMR
LRMS m/z 641 (Mꢁ Bu)þ 553, 509, 341, 283, 171; EI-HRMS calcd for
t
C26H54IO4Si3 (Mꢁ Bu)þ 641.2374, found 641.2363.
4.2.9. (2Z)-(5R,6S,7R)-5,7-Bis(tert-butyldimethylsilanyloxy)-6-[3-
(tert-butyldimethylsilanyloxy)propoxy]-3-iodonona-2,8-dien-1-ol
(9c). In the same procedure for 9a, 9c (1.88 g, 75%) was obtained
from 8c (2.07 g, 3.52 mmol), Red-AlÒ (65% toluene solution, 2.4 mL,
(100 MHz, CDCl3)
d
ꢁ4.2, ꢁ4.1, ꢁ4.0, ꢁ2.5, 14.2, 18.2, 18.3, 22.7, 25.9
(3C), 26.1 (2C), 26.3, 31.6, 51.4, 56.7, 69.7, 75.2, 80.6, 83.3, 117.0,
126.2,127.0, 131.2, 137.4,140.2; FABMS m/z 497 (MþNa)þ, HRFABMS
calcd for C27H47NaO3Si2 (MþNa)þ 497.2878, found 497.2855.
7.99 mmol), ethyl acetate (0.35 mL, 3.58 mmol), Et2O (35 mL), I2
25
(1.79 g, 7.06 mmol), and THF (10 mL). Colorless oil; [
4.46, CHCl3); IR (neat) 3331, 2930, 1254 cmꢁ1
CDCl3) 0.02 (s, 3H), 0.05 (s, 9H), 0.06 (s, 3H), 0.08 (s, 3H), 0.885 (s,
a
]
þ2.08 (c
D
4.2.6. (5R,6S,7R)-5,7-Bis(tert-butyldimethylsilanyloxy)-6-benzylnon-
8-en-2-yn-1-ol (8f). In the same procedure for 8a, 8f (1.18 g, 94%)
was obtained from 4f23e (1.18 g, 2.58 mmol), nBuLi (1.56 M hexane
;
1H NMR (400 MHz,
d
9H), 0.893 (s, 9H), 1.53 (t, J¼6.0 Hz, 1H), 1.78 (tt, J¼6.3, 6.3 Hz, 2H),
2.63 (dd, J¼14.2, 8.3 Hz, 1H), 2.78 (dd, J¼14.2, 4.3 Hz, 1H), 3.28 (dd,
J¼4.3, 3.1 Hz, 1H), 3.59 (dt, J¼9.3, 6.4 Hz, 1H), 3.66e3.77 (m, 3H),
4.06 (ddd, J¼8.3, 4.3, 3.8 Hz, 1H), 4.16 (m, 2H), 4.34 (dd, J¼7.3,
solution 2.5 mL, 3.90 mmol), paraformaldehyde (232 mg,
23
7.83 mmol), and THF (8.6 mL). Colorless oil; [
a
]
D
þ0.78 (c 2.15,
CHCl3); IR (neat) 3358, 2955, 2363, 1254, 1063 cmꢁ1 1H NMR
;