I. Dams et al. / Tetrahedron 69 (2013) 1634e1648
1647
J. Am. J. Health Syst. Pharm. 2005, 62, 691e699; (h) Collaborative Normal-Tension
Glaucoma Study Group Am. J. Ophthalmol. 1998, 126, 487e497.
4.18. Isopropyl (Z)-7-[(1R,2R,3R,5S)-3,5-dihydroxy-2-methyl-
cyclopentyl]hept-5-enoate (18)
3. (a) Ishida, N.; Odani-Kawabata, N.; Shimazaki, A.; Hara, H. Cardiovasc. Drug Rev.
2006, 24, 1e10; (b) Bean, G. W.; Camras, C. B. Surv. Ophthalmol. 2008, 53,
S69eS84; (c) Eisenberg, D. L.; Toris, C. B.; Camras, C. B. Surv. Ophthalmol. 2002, 47,
S105eS115; (d) Alm, A. Prog. Retin. Eye Res. 1998, 17, 291e312; (e) Toris, C. B.;
Gabelt, B. T.; Kaufman, P. L. Surv. Ophthalmol. 2008, 53, S107eS120; (f) Stjern-
schantz, J. W. Invest. Ophthalmol. Vis. Sci. 2001, 42, 1134e1145; (g) Brooks, T. C.;
Burlingame, M.; Burk, M.; Tortorice, K.; Dong, D.; Glassman, P. A.; Lynch, J. A.;
Good, C. B.; Rickman, H. S.; Claborn, M.; Appleman, D.; Jones, W.; Shaverd, L.
Formulary 2009, 44, 322e328; (h) Waugh, J.; Jarvis, B. Drugs Aging 2002, 19,
465e471; (i) Burk, R. M.; Woodward, D. F. Drug Dev. Res. 2007, 68, 147e155; (j)
Sharif, N. A.; Klimko, P. Expert Rev. Ophthalmol. 2009, 4, 477e489; (k) Easthope, S.
E.; Perry, C. M. Drugs Aging 2002, 19, 231e248; (l) Woodward, D. F.; Phelps, R. L.;
Krauss, A. H.-P.; Weber, A.; Short, B.; Chen, J.; Liang, Y.; Wheeler, L. A. Cardiovasc.
Drug Rev. 2004, 22, 103e120; (m) Sit, A. J.; Asrani, S. Surv. Ophthalmol. 2008, 53,
S45eS55; (n) Cantor, L. B. Exp. Opin. Invest. Drugs 2001, 10, 721e731; (o) Perry, C.
M.; McGavin, J. K.; Culy, C. R.; Ibbotson, T. Drugs Aging 2003, 20, 597e630.
4. (a) Bito, L. Z.; Draga, A.; Blanco, J.; Camras, C. B. Invest. Ophthalmol. Vis. Sci. 1983,
DBU (2.43 mL, 16.1 mmol) was added dropwise to a stirred so-
lution of acid 31 (0.78 g, 3.22 mmol) in anhydrous acetone (10 mL)
at 0 ꢁC under an argon atmosphere. The mixture was allowed to
warm to room temperature, whereupon 2-iodopropane (1.62 mL,
16.1 mmol) was added dropwise. The resulting solution was stirred
for 22 h resulting in disappearance of the starting acid 31 (TLC,
CH3CN/toluene 1:1). The reaction was quenched with ethyl acetate
(100 mL). The resulting white solid was filtered off and washed
with AcOEt (3ꢂ25 mL). The filtrate and washings were combined
and acidified with 3% citric acid solution to pH 5e6. The resulting
layers were separated and the aqueous phase was extracted with
AcOEt (3ꢂ25 mL). The combined extracts were washed with satu-
rated aqueous NaHCO3 (100 mL), water (150 mL) and dried over
anhydrous Na2SO4. Filtration and evaporation in vacuo furnished
the crude product 18 (1.14 g), which was purified by silica gel flash
chromatography with gradient elution 5e10% 2-propanol/CH2Cl2 to
afford the ester 18 (0.85 g, 93% yield, 84.4% de) as a pale yellow oil.
This sample was further purified by preparative HPLC on silica gel
to give the isopropyl ester 18 (0.62 g, 68.1% yield) as a thick col-
ꢀ
24, 312e319; (b) Giufree, G. Graefe’s Arch. Clin. Exp. Ophthalmol. 1985, 222,
139e141; (c) Camras, C. B.; Bito, L. Z.; Eakins, K. E. Invest. Ophthalmol. Vis. Sci.
1977, 16, 1125e1134; (d) Bito, L. Z. Surv. Ophthalmol. 1997, 41, S1eS14.
5. For a review on Corey synthesis of PGF2 see: (a) Corey, E. J.; Weinshenker, N.
a
M.; Schaaf, T. K.; Huber, W. J. Am. Chem. Soc. 1969, 91, 5675e5677; (b) Corey, E.
J.; Schaaf, T. K.; Huber, W.; Koelliker, U.; Weinshenker, N. M. J. Am. Chem. Soc.
1970, 92, 397e398; (c) Corey, E. J.; Noyori, R.; Schaaf, T. K. J. Am. Chem. Soc. 1970,
92, 2586e2587; (d) Corey, E. J. Angew. Chem., Int. Ed. Engl. 1991, 30, 455e465;
(e) Corey, E. J.; Cheng, X.-M. The Logic of Chemical Synthesis; Wiley: New York,
NY, 1989, pp 255e256.
ourless oil. Rf¼0.47 (CH2Cl2/i-PrOH 8:1). [
FTIR (thin film)
1312, 1247, 1180, 1109, 1040, 969, 822, 723 cmꢀ1
600 MHz)
1.06 (d, J¼7.0 Hz, 3H, ꢀCH3), 1.23 and 1.24 (two s, 6H,
eCH(CH3)), 1.31 (m, 1H, cyclopentane CH-1), 1.69 (m, 2H, -chain
a
]
20 þ31.4 (c 1.0, CH2Cl2).
ꢀ
6. Resul, B.; Stjernschantz, J.; No, K.; Liljebris, C.; Selen, G.; Astin, M.; Karlsson, M.;
D
Bito, L. Z. J. Med. Chem. 1993, 36, 243e248.
7. Selliah, R.; Dantanarayana, A.; Haggard, K.; Egan, J.; Do, E. U.; May, J. A. J. La-
belled Cpd. Radiopharm. 2001, 44, 173e183.
n
3395, 2979, 2953, 2933, 2870, 1731, 1456, 1375,
.
1H NMR (CDCl3,
d
8. Collins, P. W.; Djuric, S. W. Chem. Rev. 1993, 93, 1533e1564.
ꢀ
9. Liljebris, C.; Selen, G.; Resul, B.; Stjernschantz, J.; Hacksell, U. J. Med. Chem. 1995,
a
38, 289e304.
CH2-3), 1.76 (m, 1H, cyclopentane CH-2), 1.80 (dm, J¼15.0 Hz, 1H,
one of the cyclopentane CH2-4 group), 2.02 (ddd, J¼4.4, 6.5 and
14.5 Hz, 1H, one of the cyclopentane CH2-4 group), 2.07e2.24 (m,
10. Klimko, P.; Hellberg, M.; McLaughlin, M.; Sharif, N.; Severns, B.; Williams, G.;
Haggard, K.; Liao, J. Bioorg. Med. Chem. 2004, 12, 3451e3469.
11. Matsumura, Y.; Mori, N.; Nakano, T.; Sasakura, H.; Matsugi, T.; Hara, H.; Mor-
izawa, Y. Tetrahedron Lett. 2004, 45, 1527e1529.
12. Bowler, J.; Crossley, N. S. GB Patent 1,350,971, 1974.
13. Gutman, A.; Nisnevich, G.; Etinger, M.; Zaltzman, I.; Yudovich, L.; Pertsikov, B.;
Tishin, B. U.S. Patent 7,166,730, 2007.
14. Henegar, K. E. US Patent Application 2003/0187071 A1, 2003.
15. Hwang, S.-W.; Adiyaman, M.; Khanapure, S. P.; Rokach, J. Tetrahedron Lett. 1996,
37, 779e782.
3H,
2H,
a
-chain CH2-4 and one of the
a-chain CH2-7 group), 2.29 (m,
a-chain CH2-2), 2.87 (br s, 2H, two eOH), 2.94 (m, 1H, one of the
a
-chain CH2-7), 3.80 (m, 1H, cyclopentane CH-3), 4.15 (m, 1H,
cyclopentane CH-5), 5.00 (septet, J¼6.3 Hz, 1H, eCH(CH3)2), 5.39
(m, 1H, -chain CH-5), 5.47 (m, 1H,
-chain CH-6) ppm. 13C NMR
(150 MHz, CDCl3) 18.3 (CH3), 21.8 (2C, eCH(CH3)2), 24.9 ( -chain
C-3), 26.4 ( -chain C-7), 26.6 ( -chain C-4), 34.1 ( -chain C-2), 42.3
a
a
16. Kim, S.; Bellone, S.; Maxey, K. M.; Powell, W. S.; Lee, G.-J.; Rokach, J. Bioorg. Med.
d
a
Chem. Lett. 2005, 15, 1873e1876.
a
a
a
17. (a) Corey, E. J.; Albonico, S. M.; Koelliker, U.; Schaaf, T. K.; Varma, R. K. J. Am.
Chem. Soc. 1971, 93, 1491e1493; (b) Corey, E. J.; Becker, K. B.; Varma, R. K. J. Am.
Chem. Soc. 1972, 94, 8616e8618; (c) Corey, E. J.; Bakshi, R. K.; Shibata, S.; Chen,
C.-P.; Singh, V. K. J. Am. Chem. Soc. 1987, 109, 7925e7926; (d) Aswathanar-
ayanappa, C.; Bheemappa, E.; Bodke, Y. D. Org. Process Res. Dev. 2011, 15,
1085e1087; (e) Zanoni, G.; D’Alfonso, A.; Porta, A.; Feliciani, L.; Nolan, S. P.;
Vidari, G. Tetrahedron 2010, 66, 7472e7478; (f) Corey, E. J. Pure Appl. Chem. 1990,
(cyclopentane C-4), 47.0 (cyclopentane C-2), 52.8 (cyclopentane C-
1), 67.6 (eCH(CH3)2), 74.3 (cyclopentane C-5), 80.4 (cyclopentane
C-3), 129.4 (a-chain C-6), 129.5 (a-chain C-5), 173.4 (C]O) ppm.
HRMS (ESI): calcd for C16H28NaO4 [MþNa]þ 307.18798; found
307.1890. Chiral HPLC: AS-3R, 3
m
m, 150ꢂ4.6 mm column, H2O/
ꢀ
ꢁ
ꢀ
ꢀ ꢁ
62, 1209e1216; (g) Obadalova, I.; Pilarcík, T.; Slavíkova, M.; Hajícek, J. Chirality
2005, 17, S109eS113; (h) Hutton, J.; Senior, M.; Wright, N. C. A. Synth. Commun.
1979, 9, 799e808; (i) Hutton, J. Synth. Commun. 1979, 6, 483e486; (j) Node, M.;
Nishide, K.; Shigeta, Y.; Shiraki, H.; Obata, K. J. Am. Chem. Soc. 2000, 122,
1927e1936; (k) Noyori, R.; Tomino, I.; Yamada, M.; Nishizawa, M. J. Am. Chem.
Soc. 1984, 106, 6717e6725.
CH3CN with gradient elution 80e10%, 1.0 mL/min, tR¼15.65 min
(91.88% yield of (5Z)-(þ)-18), tR¼17.09 min (8.12% yield of (5E)-18).
LCeMS (ESI): AS-3R, 3
m
m, 150ꢂ4.6 mm column, H2O/CH3CN with
gradient elution 80e10%, 1.0 mL/min, tR¼15.39 min (m/z¼285.2
[MþH]þ for (5Z)-(þ)-18), tR¼16.95 min (m/z¼285.2 [MþH]þ for
(5E)-18).
18. Achmatowicz, B.; Baranowska, E.; Daniewski, A. R.; Pankowski, J.; Wicha, J.
Tetrahedron 1988, 44, 4989e4998.
19. Boulton, L. T.; Brick, D.; Fox, M. E.; Jackson, M.; Lennon, I. C.; McCague, R.;
Parkin, N.; Rhodes, D.; Ruecroft, G. Org. Process Res. Dev. 2002, 6, 138e145.
ꢀ
20. Das, S.; Chandrasekhar, S.; Yadav, J. S.; Gree, R. Chem. Rev. 2007, 107, 3286e3337.
ꢀꢀ
21. (a) Martynow, J. G.; Jozwik, J.; Szelejewski, W.; Achmatowicz, O.; Kutner, A.;
Acknowledgements
ꢀ
Wisniewski, K.; Winiarski, J.; Zegrocka-Stendel, O.; Go1e˛biewski, P. Eur. J. Org.
Chem. 2007, 689e703; (b) Martynow, J. G.; Szyc, J.; Szelejewski, W.; Achmato-
wicz, O.; Kutner, A.; Wisniewski, K.; Winiarski, J.; Zegrocka-Stendel, O.;
Go1e˛biewski, P. U.S. Patent 7,897,793 B2, March 1, 2011.
Financial support was provided by the European Union from the
European Regional Development Fund (ERDF) under the Innovative
Economy Operational Programme (UDA-POIG.01.03.01-14-068/
08-00).
ꢀ
22. (a) Dubiner, H. B.; Sircy, M. D.; Landry, T.; Bergamini, M. V. W.; Silver, L. H.;
Turner, F. D.; Robertson, S.; Andrew, R. M.; Weiner, A.; Przydryga, J. Clin. Ther.
2004, 26, 84e91; (b) Van der Valk, R.; Webers, C. A. B.; Schouten, J. S. A. G.;
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ꢀ
23. (a) Julia, M.; Paris, J.-M. Tetrahedron Lett. 1973, 4833e4836; (b) Kocienski, P. J.;
ꢀ
Lythgoe, B.; Ruston, S. J. Chem. Soc., Perkin Trans. 1 1978, 829e834; (c) Kocienski,
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