A. Miura, S. Kuwahara / Tetrahedron 65 (2009) 3364–3368
3367
25
d
14.0, 22.6, 25.3, 31.8, 32.8, 74.3, 76.2, 117.4, 137.7; HRMS (FAB) m/z
[
a
]
ꢀ7.03 (c 1.28, CHCl3)); IR
n
3542 (m), 3314 (br m), 1729 (s),
D
calcd for C9H18NaO2Na ([MþNa]þ) 181.1204, found 181.1212.
1250 (m), 1175 (m), 975 (m); 1H NMR (CDCl3/D2O)
d 0.89 (t,
J¼6.8 Hz, 3H), 1.26–1.56 (m, 18H), 1.58–1.64 (m, 2H), 2.30 (t,
J¼7.3 Hz, 2H), 3.45–3.49 (m, 1H), 3.67 (s, 3H), 3.94 (t, J¼6.3 Hz,
1H), 4.14 (q, J¼5.9 Hz, 1H), 5.71 (dd, J¼6.3, 15.6 Hz, 1H), 5.82 (dd,
4.1.7. Methyl (S)-9-hydroxy-10-undecenoate (3a)
To a stirred mixture of powdered 4 Å molecular sieves (10 g) in
CH2Cl2 (40 ml) was successively added diisopropyl
D
-tartrate
J¼5.9, 15.6 Hz, 1H); 13C NMR
d 14.0, 22.6, 24.8, 25.2, 25.3, 28.9,
(1.60 ml, 7.56 mmol), Ti(Oi-Pr)4 (1.86 ml, 6.30 mmol), and a solu-
tion of TBHP (ca. 5 M in toluene, 2.52 ml, 12.6 mmol) at ꢀ20 ꢂC.
After 30 min, a solution of (ꢁ)-3 (1.35 g, 6.30 mmol) in CH2Cl2
(30 ml) was added, and the resulting mixture was stirred at ꢀ20 ꢂC
for 3 days. The mixture was quenched with an ice-cooled solution
of FeSO4 (4.4 g) in 10% aq tartaric acid (15 ml), stirred for an addi-
tional 30 min, and then gradually warmed to room temperature.
After being stirred for 1 h, the mixture was filtered, and the filtrate
was concentrated in vacuo. The residue was chromatographed over
SiO2 (hexane/EtOAc¼6:1 to 2:1) to give 3a (541 mg, 80% of the
theoretical amount) as a pale yellow oil together with an epoxi-
29.1, 29.2, 31.8, 32.9, 34.0, 37.1, 51.5, 72.0, 74.6, 75.3, 129.7, 136.2,
174.4; HRMS (FAB) m/z calcd for C19H37O5 ([MþH]þ) 345.2641,
found 345.2641.
4.1.11. Methyl (9S,10E,12S,13S)-9-(tert-butyldimethylsilyl)oxy-
12,13-dihydroxy-10-octadecenoate (13b)
To a stirred solution of 2b (13.0 mg, 82.2
(81.1 mg, 0.246 mmol) in CH2Cl2 (6.5 ml) was added the second
generation Grubbs catalyst (1.7 mg, 2.0 mol) at room tempera-
ture, and the mixture was stirred at 40 ꢂC. After 2.5 h, additional
mmol) and 3b
m
catalyst (1.7 mg, 2.0 mmol) was added, and resulting mixture was
dized product (660 mg, 92% of the theoretical amount) as a color-
stirred at 40 ꢂC for another 2.5 h. The mixture was filtered, and the
filtrate was concentrated in vacuo. The residue was chromato-
graphed over SiO2 (hexane/EtOAc¼10:1 to 3:1) to give 13b (9.1 mg,
25
less oil. [
a
]
þ5.75 (c 1.00, CHCl3); IR
n
3449 (br m), 3080 (w), 1738
D
(s), 1199 (m), 1172 (m); 1H NMR
d 1.28–1.43 (m, 7H), 1.47–1.57 (m,
3H), 1.57–1.65 (m, 3H), 2.30 (t, J¼7.3 Hz, 2H), 3.67 (s, 3H), 4.09 (q,
24%) as a yellow oil together with the homodimer of 2b (6.7 mg),
22
J¼6.3 Hz, 1H), 5.10 (d, J¼10.7 Hz, 1H), 5.22 (d, J¼17.1 Hz, 1H), 5.87
and the starting material 3b (72.7 mg). [
IR
835 (m), 775 (m); 1H NMR (CDCl3/D2O)
a]
ꢀ11.9 (c 0.13, CHCl3);
D
(ddd, J¼6.3, 10.7, 17.1 Hz, 1H); 13C NMR
d
24.9, 25.2, 29.0, 29.1, 29.3,
n
3410 (br m), 1742 (s), 1251 (m), 1198 (w), 1172 (w), 971 (w),
0.03 (s, 3H), 0.05 (s, 3H),
34.1, 37.0, 51.5, 73.2, 114.6, 141.3, 174.3; HRMS (FAB) m/z calcd for
C12H23O3 ([MþH]þ) 215.1647, found 215.1644.
d
0.89 (s, 9H), 0.89 (t, J¼6.6 Hz, 3H), 1.25–1.53 (m, 20H), 1.60–1.62
(m, 2H), 2.30 (t, J¼7.3 Hz, 2H), 3.43 (dt, J¼2.4, 6.8 Hz, 1H), 3.67 (s,
3H), 3.90 (t, J¼6.8 Hz, 1H), 4.12 (dt, J¼5.9, 6.3 Hz, 1H), 5.59 (dd,
J¼6.8, 15.6 Hz, 1H), 5.75 (dd, J¼5.9, 15.6 Hz, 1H); 13C NMR (CDCl3)
4.1.8. Determination of the enantiomeric excess of 3a
Compound 3a was converted into the corresponding (R)- and
(S)-MTPA esters (9) by treating with (S)- and (R)-MTPACl, re-
spectively, in pyridine. The 1H NMR signal for the olefinic proton at
the C10 position of the (R)-MTPA ester was observed at 5.72 ppm
(ddd, J¼6.8,10.7,17.6 Hz), while that of the (S)-MTPA ester appeared
at 5.82 ppm (ddd, J¼7.3, 10.3, 17.6 Hz). In each spectrum of the di-
astereomeric MTPA esters, no signal due to the corresponding di-
astereomer was observed. Therefore, compound 3a was estimated
to be optically pure within the limit of NMR detection.
d
ꢀ4.8, ꢀ4.4, 14.0, 18.2, 22.6, 24.8, 25.0, 25.2, 25.9, 29.0, 29.1, 29.3,
31.9, 32.9, 34.1, 38.1, 51.5, 72.6, 74.7, 75.7, 128.4, 137.2, 174.4; HRMS
(FAB) m/z calcd for C25H50O5SiNa ([MþNa]þ) 481.3325, found
481.3324.
4.1.12. (9S,10E,12S,13S)-9,12,13-Trihydroxy-10-
octadecenoic acid (1)
To a stirred solution of 13a (10.5 mg, 30
(0.140 ml) was added 1 M NaOH aq (35 l, 35
mixture was stirred at 40 ꢂC for 5 h. The mixture was quenched
with 1 M HCl aq (35
l) at 0 ꢂC and extracted with EtOAc. The
mmol) in MeOH
m
mmol) and the
4.1.9. Methyl (S)-9-(tert-butyldimethylsilyl)oxy-10-
undecenoate (3b)
m
To a stirred solution of 3a (63.1 mg, 0.294 mmol) in DMF (0.5 ml)
were added imidazole (60.1 mg, 0.883 mmol) and TBSCl (66.5 mg,
0.442 mmol) at 0 ꢂC. The mixture was gradually warmed to room
temperature over 4 h, quenched with brine, and then extracted
with ether. The extract was washed with water, dried (MgSO4), and
concentrated in vacuo. The residue was chromatographed over SiO2
extract was washed with brine, dried (MgSO4), and concentrated
in vacuo. The residue was chromatographed over SiO2 (CHCl3/
MeOH¼10:1) to give 1 (8.5 mg, 85%) as a white solid. Mp 103.5–
25
104.0 ꢂC (lit.8 mp 104–106 ꢂC, lit.11 mp 104–106 ꢂC); [
a
]
D
ꢀ9.8 (c
28
25
0.30, MeOH) (lit.5 [
a
]
ꢀ8.1 (c 0.32, MeOH), lit.8 [
a
]
ꢀ8.0 (c 0.30,
D
D
25
MeOH), lit.11
[
a
]
ꢀ7.9 (c 0.30, MeOH)); IR
n 3543 (m), 3317 (br m),
D
(hexane/EtOAc¼100:1) to give 3b (82.8 mg, 86%) as a pale yellow
2954 (w), 2921 (s), 2846 (s), 1693 (s), 1461 (w), 1070 (w), 974 (w);
23
oil. [
a]
ꢀ6.00 (c 1.00, CHCl3); IR
n
1742 (s), 1252 (m), 1199 (w), 1171
1H NMR (CD3OD)
d
0.91 (t, J¼6.8 Hz, 3H), 1.25–1.43 (m, 14H), 1.44–
D
(w), 836 (m), 775 (m); 1H NMR (CDCl3)
d
0.03 (s, 3H), 0.05 (s, 3H),
1.63 (m, 6H), 2.26 (t, J¼7.3 Hz), 3.38–3.43 (m, 1H), 3.90 (t, J¼5.4 Hz,
1H), 4.04 (q, J¼5.4 Hz, 1H), 5.67 (dd, J¼5.4, 15.6 Hz, 1H), 5.71 (dd,
0.89 (s, 9H), 1.29 (m, 8H), 1.40–1.50 (m, 2H), 1.62 (m, 2H), 2.30 (t,
J¼7.3 Hz, 2H), 3.67 (s, 3H), 4.09 (dt, J¼5.9, 6.3 Hz, 1H), 5.01 (d,
J¼10.3 Hz, 1H), 5.12 (d, J¼17.1 Hz, 1H), 5.79 (ddd, J¼6.3, 10.3, 17.1 Hz,
J¼5.4, 15.6 Hz, 1H); 13C NMR (CD3OD)
d 14.5, 23.8, 26.3, 26.5, 26.7,
30.3, 30.5, 30.6, 33.2, 33.6, 35.5, 38.4, 73.1, 75.8, 76.6, 131.1, 136.6,
178.4; HRMS (FAB) m/z calcd for C18H35O5Na ([MþNa]þ) 353.2304,
found 353.2307.
1H); 13C NMR
d
ꢀ4.8, ꢀ4.4,18.3, 24.9, 25.1, 25.9 (3C), 29.1, 29.2, 29.4,
34.1, 38.0, 51.4, 73.8, 113.4, 141.9, 174.3; HRMS (FAB) m/z calcd for
C18H36O3SiNa ([MþNa]þ) 351.2331, found 351.2334.
Acknowledgements
4.1.10. Methyl (9S,10E,12S,13S)-9,12,13-trihydroxy-10-
octadecenoate (13a)
To a stirred solution of 2b (20.0 mg, 0.126 mmol) and 3a
(81.2 mg, 0.379 mmol) in CH2Cl2 (2.5 ml) was added the second
We thank Ms. Yamada (Tohoku University) for measuring NMR
and mass spectra. This work was supported, in part, by a Grant-in-
Aid for Scientific Research (B) from the Ministry of Education,
Culture, Sports, Science and Technology of Japan (No. 19380065).
generation Grubbs catalyst (5.4 mg, 6.3 mmol) at room tempera-
ture, and the mixture was stirred at 40 ꢂC for 5 h. The mixture was
filtered, and the filtrate was concentrated in vacuo. The residue
was chromatographed over SiO2 (hexane/EtOAc¼1:1) to give 13a
(14.8 mg, 35%) as a white solid together with the homodimer of 2b
Supplementary data
1H and 13C NMR spectra of compounds 4–8, 2a, 2b, 3a, 3b, 9, 13a,
13b, and 1. Supplementary data associated with this article can be
(9.6 mg), the homodimer of 3a (32.3 mg), and the starting mate-
26
rial 3a (26.0 mg). Mp 92.5–93.0 ꢂC; [
a]
ꢀ9.00 (c 0.60, CHCl3) (lit.3
D