4
Tetrahedron Letters
[6] B. H. Lipshutz, M. R. Wood, J. Am. Chem. Soc. 116 (1994)
Conclusion
11689–11702.
[7] M. Suzuki, H. Koyama, R. Noyori, Bull. Chem. Soc. Jpn.
77 (2004) 259–268.
In this study, we have established a stoichiometric three
-component coupling for the general synthesis of PGs and stable
PGI2 analogs via a combination of organozinc-aided conjugate
addition and propargylation with an organotriflate without the
use of heavy metals or carcinogenic HMPA. We hope that this
highly convergent C-coupling will contribute to advances in
chemical syntheses and interdisciplinary bio-medical sciences.
[8] Experimental procedure: To a 50-mL ampoule-type flask
(see ref.[4b]) was added 7 (266 mg, 0.500 mmol) in THF
(1.5 mL) under an argon atmosphere and cooled to –85°C
using a liquid nitrogen/methanol bath. Then, a solution of
n-butyllithium (1.55 M hexane, 0.323 mL, 0.500 mmol)
was added. After the mixture was stirred for 1 h at –85°C,
dimethylzinc (1.0 M hexane, 0.50 mL, 0.50 mmol) was
added from the inlet with the spiral tube maintained at –
85°C. After stirring for 10 min at this temperature, 2 (106
mg, 0.500 mmol) in THF (1.5 mL) was added through the
cooled (–85°C) spiral tube over a period of 10 min, and the
spiral tube was then rinsed with THF (1.0 mL). After
stirring at –85 °C for 1 h, 9 (prepared by a similar protocol
as in ref.[6]) in hexane/diethyl ether solution, which was
then transferred at –78°C using a cannula into the flask
containing the enolate prepared by the above conjugate
addition. After stirring for 2 h at –78 °C, the reaction was
quenched with a sat. aq. NH4Cl solution (5 mL). After
extraction with diethyl ether (3 × 5 mL) followed by
concentration, flash chromatography on silica gel using
20:1 hexane/ethyl acetate afforded 6 (260.5 mg, 88%) as a
colorless oil.
Acknowledgements
This research was supported in part by Grant-in-Aids for
Creative Scientific Research (No. 13NP0401) from the Ministry
of Education, Culture, Sports, Science and Technology (MEXT)
of Japan. We thank Dr. T. Hosoya and Mr. K. Komori for their
assistance at an early stage of the study, particularly for the
synthesis of -side chain unit 23. We would also like to thank
Ms. K. Yamashita for her assistance to supply -side chain units
and for 1H and 13C NMR measurements at a late stage of the
study. We would like to thank Enago for English language
editing.
Supplementary data
[9] M. Suzuki, K. Kato, R. Noyori, Yu. Watanabe, H. Takechi,
K. Matsumura, B. Långström, Y. Watanabe, Angew. Chem.
Int. Ed. 35 (1996) 334–336.
Supplementary data to this article can be found online at
References and notes
[10] M. Suzuki, K. Kato, Yu. Watanabe, T. Satoh, K.
Matsumura, Y. Watanabe, R. Noyori, Chem. Commun.
(1999) 307–308.
[11] (a) T. Satoh, Y. Ishikawa, Y. Kataoka, Y. Cui, H. Yanase,
K. Kato, Yu. Watanabe, K. Matsumura, H. Hatanaka, K.
Kataoka, R. Noyori, M. Suzuki, Y. Watanabe, Eur. J.
Neurosci. 11 (1999) 3115–3124;
[1] J. R. Vane, Angew. Chem. Int. Ed. 22 (1983) 741–752;
B. Samuelsson, Angew. Chem. Int. Ed. 22 (1983) 805–815;
S. Bergström, Angew. Chem. Int. Ed. 22 (1983) 858–866.
[2] E. J. Corey, Angew. Chem. Int. Ed. 30 (1991) 455–465;
See also the synthesis of PGs via Corey’s lactone by the
Upjohn Company: R. C. Kelly, V. VanRheenen, I.
Schletter, M. D. Pillai, J. Am. Chem. Soc. 95 (1973) 2746–
2747;
(b) Y. Cui, Y. Kataoka, T. Satoh, A. Yamagata, N.
Shirakawa, Yu. Watanabe, M. Suzuki, H. Yanase, K.
Kataoka, Y. Watanabe, Biochem. Biophys. Res. Commun.
265 (1999) 301–304;
R. Kelly, V. VanRheenen, Tetrahedron Lett. 14 (1973)
1709–1712;
(c) M. Suzuki, R. Noyori, B. Långström, Y. Watanabe,
Bull. Chem. Soc. Jpn. 73 (2000) 1053–1070.
R. C. Kelly, V. VanRheenen, Tetrahedron Lett. 17 (1976)
1067–1070.
[12] The aldehyde intermediate can also be synthesized by
deprotection (AcOH-H2O) of the corresponding THP-
protected aldehyde derived from Corey’s lactone [2]. See:
M. Sodeoka, M. Shibasaki, Chem. Lett. (1984) 579-582.
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Watanabe, Trends Anal. Chem. 23 (2004) 595–607;
(b) M. Suzuki, H. Doi, H. Koyama, Z. Zhang, T. Hosoya,
H. Onoe, Y. Watanabe, Chem. Rec. 14 (2014) 516–541.
[3] (a) R. Noyori, M. Suzuki, Angew. Chem. Int. Ed. 23 (1984)
847–876;
(b) R. Noyori, M. Suzuki, Chemtracts-Org. Chem. 3 (1990)
173–197.
[4] (a) M. Suzuki, A. Yanagisawa, R. Noyori, J. Am. Chem.
Soc. 107 (1985) 3348–3349;
(b) M. Suzuki, A. Yanagisawa, R. Noyori, J. Am. Chem.
Soc. 110 (1988) 4718–4726;
(c) Y. Morita, M. Suzuki, R. Noyori, J. Org. Chem. 54
(1989) 1785–1787;
(d) M. Suzuki, Y. Morita, H. Koyano, M. Koga, R. Noyori,
Tetrahedron 46, (1990) 4809–4822.
For application of the enolate/HMPA/dimethylzinc system
by other groups, see: (e) M. Ichikawa, M. Takahashi, S.
Aoyagi, C. Kibayashi, J. Am. Chem. Soc. 126 (2004)
16553–16558;
[14] 24: 13C NMR (acetone-d6, 100 MHz, 25 °C, TMS)
–
4.88, –4.41, –4.23 (2C), 17.20, 18.47, 18.58, 18.70, 21.42,
25.15, 26.23 (3C), 26.28 (3C), 33.13, 45.98, 48.15, 51.58,
53.13, 53.22, 73.56, 75.37, 78.32, 81.59, 127.53, 127.77,
128.72, 130.20, 131.69, 137.26, 137.99, 139.53, 173.67,
212.83 ppm; HRMS (EI+, 100% acetone): m/z: calcd for
C32H49O5Si2 ([M-C4H9]+) 569.3119; found, 569.3149.
[15] 27: 13C NMR (CDCl3, 100 MHz, 25 °C, TMS)
–
(f) A. Fürtner, P. W. Davies, Chem. Commun. (2005)
2307–2320;
4.63 (2C), 16.69, 18.14, 18.19, 21.40, 24.16, 25.74 (3C),
32.78, 34.63, 35.76, 47.58, 51.51, 52.82, 53.01, 72.98,
77.46, 80.72, 125.42, 126.60, 128.22, 129.25, 129.86,
133.37, 137.85, 141.72, 173.68, 213.90 ppm; HR-MS (EI+,
100% acetone): m/z: calcd for C26H35O4Si ([M-C4H9]+)
439.2305; found, 439.2322.
(g) G. B. Dudley, D. A. Engel, I. Ghiviriga, H. Lam, K. W.
C. Poon, J. A. Singletary, Org. Lett. 9 (2007) 2839–2842.
[5] (a) O. W. Gooding, J. Org. Chem. 55 (1990) 4209–4211;
(b) O. W. Gooding, C. C. Beard, G. F. Cooper, D. Y.
Jackson, J. Org. Chem. 58 (1993) 3681–3686.
[16] M. Suzuki, H. Koyano, R. Noyori, J. Org. Chem. 52 (1987)
5583–5588.