T. Shirahata et al. / Tetrahedron 62 (2006) 9483–9496
9491
a colorless oil. Rf¼0.47 (silica gel, hexane/AcOEt¼4:1); IR
(KBr) n cmꢀ1: 1730; 1H NMR (270 MHz, CDCl3) d: 3.18 (t,
J¼7.3 Hz, 2H), 2.20 (t, J¼7.6 Hz, 2H), 1.76–1.87 (complex
m, 2H), 1.53–1.60 (complex m, 2H), 1.44 (s, 9H), 1.26–1.41
(complex m, 6H); 13C NMR (67.5 MHz, CDCl3) d: 173.0,
79.8, 35.4, 33.3, 30.2, 29.0, 28.7, 28.1, 28.0 (3C), 24.9;
HRMS (EI) m/z: 326.0763 [M]+, Calcd for C12H23O2I:
326.0743 [M].
11.0 mmol), K3[Fe(CN)6] (264.4 mg, 0.803 mmol), K2CO3
(110.8 mg, 0.803 mmol), and K2OsO4$2H2O (4.0 mg,
0.011 mmol) in t-BuOH/H2O (1:1) (2.6 mL) was treated
with methanesulfonamide (25.5 mg, 0.268 mmol) at ambient
temperature. The clear yellow solution was cooled to 0 ꢁC
and 11 (117.8 mg, 0.268 mmol) was added. The solution
was stirred vigorously at 0 ꢁC for 40 h 50 min and then
quenched with solid Na2SO3 (50 mg), warmed to ambient
temperature, and stirred for further 30 min. The resultant
mixture was extracted with CHCl3 (5 mLꢂ3). The organic
layer was washed with satd aq NaCl (5 mL), dried over
Na2SO4, filtered, and concentrated. The residue was purified
by column chromatography (hexane/AcOEt¼1:1) to give
(ꢀ)-12 (81.2 mg, 64%, 95% ee) as a colorless oil. Rf¼0.38
(silica gel, hexane/AcOEt¼1:1); [a]2D4 ꢀ4.5 (c 1.08,
7.3.1.3. (E,E)-1-(1,3-Dithian)-2,4-decadiene (10). To
a solution of (E,E)-2,4-decadienal (9, 21.4 g, 25.0 mL,
141 mmol) in CH2Cl2 (140 mL) at 0 ꢁC were added 1,3-
propanedithiol (18.3 g, 17.0 mL, 169 mmol) and BF3$Et2O
(3.92 g, 3.40 mL, 27.6 mmol), and then the reaction mixture
was warmed up to rt, stirred for 12 h. The resulting mixture
was treated with satd aq NaHCO3 (200 mL) and extracted
with CHCl3 (100 mLꢂ3). The organic layer was washed
with satd aq NaCl (100 mL), dried over Na2SO4, filtered, and
concentrated. The residue was purified by column chromato-
graphy (hexane/AcOEt¼100:1) to give 10 (32.7 g, 96%) as a
colorless oil. Rf¼0.52 (silica gel, hexane/AcOEt¼5:1); IR
1
CHCl3); IR (KBr) n cmꢀ1: 3421, 1730, 1628; H NMR
(270 MHz, CDCl3) d: 5.91 (dd, J¼15.5, 6.6 Hz, 1H), 5.75
(d, J¼15.5 Hz, 1H), 4.04 (dd, J¼6.6, 5.3 Hz, 1H), 4.01–
3.00 (m, 1H), 2.87 (ddd, J¼14.2, 11.5, 2.6 Hz, 2H), 2.68–
2.63 (m, 2H), 2.35 (br s, 1H), 2.26 (br s, 1H), 2.19 (t,
J¼7.3 Hz, 2H), 2.06–2.01 (m, 2H), 1.93–1.88 (m, 2H),
1.67–1.28 (complex m, 18H), 1.44 (s, 9H), 0.89 (t,
J¼6.6 Hz, 3H); 13C NMR (67.5 MHz, CDCl3) d: 173.8,
136.5, 133.6, 80.4, 75.9, 75.1, 54.7, 42.4, 35.9, 33.5, 32.3,
29.8, 29.4, 29.3, 28.5 (3C), 27.5 (2C), 25.8, 25.6, 25.4,
24.0, 22.9, 14.4; HRMS (FAB, NaI matrix), m/z: 497.2743
[M+Na]+, Calcd for C25H46O4S2Na: 497.2735 [M+Na].
1
(KBr) n cmꢀ1: 1653; H NMR (270 MHz, CDCl3) d: 6.34
(dd, J¼15.2, 10.6 Hz, 1H), 5.99 (dd, J¼15.2, 10.6 Hz, 1H),
5.73 (dt, J¼15.2, 7.2 Hz, 1H), 5.59 (dd, J¼15.2, 7.9 Hz, 1H),
4.66 (d, J¼7.9 Hz, 1H), 2.96–2.79 (complex m, 4H), 2.23–
2.02 (complex m, 3H), 1.91–1.77 (m, 1H), 1.39–1.19 (com-
plex m, 6H), 0.87 (t, J¼6.9 Hz, 3H); 13C NMR (67.5 MHz,
CDCl3) d: 137.3, 133.9, 128.8, 126.8, 47.6, 32.8, 31.3, 30.2
(2C), 29.0, 25.1, 22.5, 14.0; HRMS (EI) m/z: 242.1169 [M]+,
Calcd for C13H22O2: 242.1163 [M].
7.3.2.2.
(12S,13S)-(E)-9-(1,3-Dithian)-12,13-di-tert-
butyldimethylsiloxy-10-octadecaenoic acid-tert-butyl ester
((L)-13). To a solution of (ꢀ)-12 (372 mg, 0.787 mmol)
in CH2Cl2 (7.9 mL) were added 2,6-lutidine (916 mL,
7.87 mmol) and TBSOTf (900 mL, 3.93 mmol) at ꢀ78 ꢁC.
The reaction mixture was stirred at ꢀ78 ꢁC for 30 min.
The resultant mixture was treated with H2O (1 mL) and
extracted with CHCl3 (5 mLꢂ3). The organic layer was
washed with satd aq NaCl (5 mL), dried over Na2SO4, fil-
tered, and concentrated. The residue was purified by column
chromatography (hexane/AcOEt¼100:1) to give (ꢀ)-13
(489 mg, 89%) as a colorless oil. Rf¼0.60 (silica gel, hex-
ane/AcOEt¼1:1); [a]D24 ꢀ24.1 (c 1.01, CHCl3); IR (KBr)
7.3.1.4. (E,E)-9-(1,3-Dithian)-10,12-octadecadienoic
acid-tert-butyl ester (11). To a solution of 10 (200 mL,
206 mg, 0.851 mmol) in THF (8.5 mL) was added n-BuLi
(1.53 M solution in hexane, 612 mL, 0.936 mmol) at ꢀ78 ꢁC
dropwise (ca. 15 min). The resulting mixture was stirred
at ꢀ78 ꢁC for 1 h followed by the addition of 8 (327 mL,
416 mg, 1.28 mmol) in one portion. The reaction mixture
was stirred at ꢀ78 ꢁC for 1 h, after that time, the solution
was treated with satd aq NH4Cl (10 mL) and extracted with
AcOEt (10 mLꢂ3). The organic layer was washed with satd
aq NaCl (10 mL), dried over Na2SO4, filtered, and concen-
trated. The residue was purified by column chromatography
(hexane/AcOEt¼100:1) to give 11 (318 mg, 85%) as a color-
less oil. Rf¼0.36 (silica gel, hexane/AcOEt¼20:1, twice); IR
(KBr) n cmꢀ1: 1730, 1695; 1H NMR (400 MHz, CDCl3) d:
6.39 (dd, J¼15.2, 10.4 Hz, 1H), 6.12 (dd, J¼14.9, 10.4 Hz,
1H), 5.76 (dt, J¼14.9, 7.2 Hz, 1H), 5.54 (d, J¼15.2 Hz, 1H),
2.88 (ddd, J¼14.0, 11.2, 2.5 Hz, 2H), 2.64 (ddd, J¼14.0,
5.2, 3.0 Hz, 2H), 2.18 (t, J¼7.2 Hz, 2H), 2.12–2.06 (m, 2H),
2.05–1.98, 1.93–1.91 (m, 1H each), 1.82–1.78 (m, 2H), 1.59–
1.52 (m, 2H), 1.47–1.36 (complex m, 4H), 1.44 (s, 9H), 1.34–
1.19 (complex m, 10H), 0.89 (t, J¼7.1 Hz, 3H); 13C NMR
(100.6 MHz, CDCl3) d: 173.2, 135.5, 133.8, 133.6, 129.0,
79.8, 54.9, 42.3, 35.5, 32.6, 31.4, 29.5, 29.0 (2C), 28.9, 28.1
(3C), 27.2 (2C), 25.5, 25.0, 23.7, 22.5, 14.0; HRMS (EI)
m/z: 440.2779 [M]+, Calcd for C25H44O2S2: 440.2783 [M].
1
n cmꢀ1: 3442, 1731, 1630; H NMR (270 MHz, CDCl3)
d: 5.98 (dd, J¼15.2, 6.6 Hz, 1H), 5.59 (d, J¼15.8 Hz, 1H),
4.24 (m, 1H), 3.59 (m, 1H), 2.98–2.87 (complex m, 1H),
2.86–2.64 (complex m, 2H), 2.18 (t, J¼7.3 Hz, 2H), 2.00–
1.87 (complex m, 2H), 1.80 (m, 2H), 1.44 (s, 9H), 1.67–
1.14 (complex m, 18H), 0.91–0.86 (complex m, 21H),
0.11–0.03 (m, 12H); 13C NMR (67.5 MHz, CDCl3) d:
173.3, 133.4, 133.0, 79.9, 75.5, 75.0, 55.0, 42.3, 35.6, 31.9,
31.1, 29.6, 29.1 (2C), 28.1 (3C), 27.1, 27.0, 26.0, 25.8
(3C), 25.7, 25.1, 23.7, 22.5, 18.2, 18.0, 14.0, ꢀ4.1, ꢀ4.6
(2C), ꢀ4.8; HRMS (FAB, NBA matrix), m/z: 701.4539
[M]+, Calcd for C37H74O4Si2S2: 702.4534 [M].
7.3.2.3. (12S,13S)-(E)-9-Oxo-12,13-di-tert-butyldimethyl-
siloxy-10-octadecaenoic acid-tert-butyl ester ((L)-14).
To a mixture of (ꢀ)-13 (494 mg, 0.704 mmol) and CaCO3
(141 mg, 1.41 mmol) in THF (14 mL) was added a solution
of Hg(ClO4)3 (638 mg, 1.41 mmol) in H2O (2.8 mL) drop-
wise. The resultant mixture was stirred at rt for 30 min,
and then diluted with ether (5 mL). This mixture was filtered
through Celite. The residue was concentrated and dissolved
in CHCl3 (5 mL). This solution was washed with satd aq
7.3.2. Synthesis of (9S,12S,13S)-(E)-9,12,13-trihydroxy-
10-octadienoic acid ((L)-4).
7.3.2.1. (12S,13S)-(E)-12,13-Dihydroxy-9-(1,3-dithian)-
10-octadecaenoic acid-tert-butyl ester ((L)-12). A well-
stirred solution of (DHQ)PHAL(DHQ)Me+$Iꢀ(10.0 mg,