LETTER
Synthesis of (S,5Z,8E,10E)-12-Hydroxyheptadeca-5,8,10-trienoic Acid
1547
1) n-BuLi, THF
2) BF3⋅Et2O
H2, Lindlar cat.
OTBS
OTBS
HO
OTBS
HO
quinoline, EtOAc
98%
3) ethylene oxide
85%
17
19
18
1) TsCl, Et3N, DMAP, CH2Cl2
Ph3P, MeCN
96%
I
OTBS
I– Ph3P+
OTBS
2) NaI, acetone
91%
20
21
OTBDPS
OTBDPS
OTBDPS
DIBAL-H, toluene
21, NaN(TMS)2
CuCN
H
11C5
I
H11C5
CN
H11C5
CHO
NMP, 130 °C
97%
–78 °C
83%
THF
82%
(S)-7
22
23
OTBDPS
OTBDPS
PPTS (1.2 equiv)
OTBS
OH
H11C5
H11C5
CH2Cl2–EtOH
64%
24
25
1) PCC
2) NaClO2, isoprene
OR
H11C5
COOH
buffer (pH 3.6), t-BuOH
26, R = OTBDPS
(8Z)-isomer 3, R = OH
TBAF
90%
42%
similarly,
OTBDPS
(8Z,12R)-isomer 4
H11C5
I
(R)-7
Scheme 2 Syntheses of (8Z)-isomer 3 and (8Z,12R)-isomer 4
N.; Noyori, R. J. Org. Chem. 1989, 54, 5292. (c) Russell, S.
W.; Pabon, H. J. J. J. Chem. Soc., Perkin Trans. 1 1982, 545.
(d) Greé, R.; Tourbah, H.; Carrié, R. Tetrahedron Lett. 1986,
27, 4983. (e) De Montarby, L.; Tourbah, H.; Greé, R. Bull.
Chim. Soc. Fr. 1989, 419. (f) Nicolaou, K. C.; Stylianides,
N. A.; Ramphal, J. Y. J. Chem. Soc., Perkin Trans. 1 1989,
2131.
References and Notes
(1) (a) Yokomizo, T. Adv. Enzyme Regul. 2011, 51, 59.
(b) Brink, C.; Dahlén, S.-E.; Drazen, J.; Evans, J. F.; Hay, D.
W. P.; Nicosia, S.; Serhan, C. N.; Shimizu, T.; Yokomizo, T.
Pharmacol. Rev. 2003, 55, 195. (c) Tager, A. M.; Luster, A.
D. Prostaglandins Leukotrienes Essent. Fatty Acids 2003,
69, 123.
(2) (a) Yokomizo, T.; Izumi, T.; Chang, K.; Takuwa, Y.;
Shimizu, T. Nature 1997, 387, 620. (b) Yokomizo, T.; Kato,
K.; Terawaki, K.; Izumi, T.; Shimizu, T. J. Exp. Med. 2000,
192, 421.
(7) (a) Agins, A.; Thomas, M. J.; Edmonds, C. G.; McCloskey,
J. A. Biochem. Pharmacol. 1987, 36, 1799. (b) Liu, Y.;
Yoden, K.; Shen, R.-F.; Tai, H.-H. Biochem. Biophys. Res.
Commun. 1985, 129, 268.
(8) (a) Ogawa, N.; Kobayashi, Y. Tetrahedron Lett. 2009, 50,
6079. (b) Kosaki, Y.; Ogawa, N.; Kobayashi, Y.
Tetrahedron Lett. 2010, 51, 1856. (c) Ogawa, N.;
Kobayashi, Y. Tetrahedron Lett. 2011, 52, 3001.
(9) (a) Gao, Y.; Klunder, J. M.; Hanson, R. M.; Ko, S. Y.;
Masamune, H.; Sharpless, K. B. J. Am. Chem. Soc. 1987,
109, 5765. (b) Kitano, Y.; Matsumoto, T.; Sato, F.
Tetrahedron 1988, 44, 4073.
(10) Matsumura, K.; Hashiguchi, S.; Ikariya, T.; Noyori, R. J.
Am. Chem. Soc. 1997, 119, 8738.
(11) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
(12) Kitano, Y.; Matsumoto, T.; Wakasa, T.; Okamoto, S.;
Shimazaki, T.; Kobayashi, Y.; Sato, F. Tetrahedron Lett.
1987, 28, 6351.
(3) Okuno, T.; Iizuka, Y.; Okazaki, H.; Yokomizo, T.; Taguchi,
R.; Shimizu, T. J. Exp. Med. 2008, 205, 759.
(4) (a) Iizuka, Y.; Yokomizo, T.; Terawaki, K.; Komine, M.;
Tamaki, K.; Shimizu, T. J. Biol. Chem. 2005, 280, 24816.
(b) Yasuda, D.; Okuno, T.; Yokomizo, T.; Hori, T.; Hirota,
N.; Hashidate, T.; Miyano, M.; Shimizu, T.; Nakamura, M.
FASEB J. 2009, 23, 1470. (c) Iizuka, Y.; Okuno, T.; Saeki,
K.; Uozaki, H.; Okada, S.; Misaka, M.; Sato, T.; Toh, H.;
Fukayama, M.; Takeda, N.; Kita, Y.; Shimizu, T.;
Nakamura, A.; Yokomizo, T. FASEB J. 2010, 24, 4678.
(5) (a) Hamberg, M.; Samuelsaon, B. Proc. Natl. Acad. Sci.
U.S.A. 1974, 71, 3400. (b) Hamberg, M.; Svensson, J.;
Samuelsson, B. Proc. Natl. Acad. Sci. U.S.A. 1974, 71, 3824.
(c) Shimizu, T.; Kondo, K.; Hayaishi, O. Arch. Biochem.
Biophys. 1981, 206, 271.
(13) The Noyori reduction of acetylene ketone i afforded alcohol
ii with 96% ee by chiral HPLC of the derived benzoate.
However, hydrostannation of the TBDPS ether iii under
(6) (a) Suzuki, M.; Noyori, R. J. Am. Chem. Soc. 1982, 104,
2024. (b) Suzuki, M.; Ohtake, H.; Kameya, Y.; Hamanaka,
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Synlett 2013, 24, 1545–1548