A. Niidu et al. / Tetrahedron: Asymmetry 17 (2006) 2678–2683
2683
by flash chromatography (silica gel, DCM/MeOH, 15:1–
5. (a) Hancock, A. J.; Lister, M. D.; Sable, H. Z. J. Lipid Res.
982, 23, 183–189; (b) Pajouhesh, H.; Hancock, A. J. J. Lipid
1
10:1) to yield a mixture of two isomers as oil (9.7 mg,
0.073 mmol, 88%): (1S,2S,3R)-1-methyl-cyclopentane-
1,2,3-triol 11 and (1S,2S,3S)-1-methyl-cyclopentane-1,2,3-
Res. 1984, 25, 310–312; (c) Barlow, P. N.; Lister, M. D.;
Sigler, P. B.; Dennis, E. A. J. Biol. Chem. 1988, 263, 12954–
1
2958.
triol 12 in 3:2 ratio by proton NMR. Compound 11:
6
7
. Gulick, R. M. Clin. Microbiol. Infect. 2003, 9, 186–193.
. (a) Agrofoglio, L.; Suhas, E.; Farese, A.; Condom, R.;
Challand, S. R.; Earl, R. A.; Guedj, R. Tetrahedron 1994, 50,
(
500 MHz, DMSO-d ): d 1.02 (s, 3H, 1-CH ), 1.44 (m,
6 3
1
1
1
H, H-4), 1.48 (m, 1H, H-5), 1.63 (m, 1H, H-5), 1.77 (m,
H, H-4), 3.42 (t, 1H, H-2), 3.63 (m, 1H, H-3), 4.32 (s,
1
0611–10670; (b) Crimmins, M. T. Tetrahedron 1998, 54,
1
3
H, 1-OH), 4.62 (d, 1H, 3-OH), 4.67 (d, 1H, 2-OH);
C
9229–9272; (c) Borthwick, A.; Biggadike, K. Tetrahedron
1992, 48, 571–623; (d) Huryn, D. M.; Okabe, M. Chem. Rev.
1992, 92, 1745–1768.
NMR (125 MHz, DMSO-d ): d 23.27 (1-CH ), 29.25 (C-
6
3
4
), 36.27 (C-5), 76.87 (C-3), 77.63 (C-1), 85.08 (C-2). Com-
1
8
. Gurjar, M. K.; Maheshwar, K. J. Org. Chem. 2001, 66, 7552–
pound 12: H NMR (500 MHz, DMSO-d ): d 1.14 (s, 3H,
6
7
554.
1
-CH ), 1.39 and 1.64 (m, 2H, H-5), 1.39 and 1.87 (m, 2H,
3
9
. (a) Kim, H. O.; Yoo, S. J.; Ahn, H. S.; Choi, W. J.; Moon, H.
R.; Lee, K. M.; Chun, M. W.; Jeong, L. S. Bioorg. Med.
Chem. Lett. 2004, 14, 2091–2093; (b) Jeong, L. S.; Yoo, S. J.;
Lee, K. M.; Koo, M. J.; Choi, W. J.; Kim, H. O.; Moon, H.
R.; Lee, M. Y.; Park, J. G.; Lee, S. K.; Chun, M. W. J. Med.
Chem. 2003, 46, 201–203.
H-4), 3.31 (m, 1H, H-2), 4.17 (m, 1H, H-3), 4.22 (d,
J = 4.1 Hz, 1H, 2-OH), 4.24 (s, 1H, 1-OH), 4.32 (d,
1
3
J = 7.0 Hz, 1H, 3-OH); C NMR (125 MHz, DMSO-d6):
d 23.90 (1-CH ), 29.91 (C-4), 35.88 (C-5), 71.96 (C-3),
3
7
8.71 (C-1), 79.23 (C-2).
1
1
0. (a) Choi, W. J.; Park, J. G.; Yoo, S. J.; Kim, H. O.; Moon, H.
R.; Chun, M. W.; Jung, Y. H.; Jeong, L. S. J. Org. Chem.
2001, 66, 6490–6494; (b) Hong, J. H.; Shim, M. J.; Ro, B. O.;
Ko, O. H. J. Org. Chem. 2002, 67, 6837–6840; (c) Battistini,
L.; Curti, C.; Zanardi, F.; Rassu, G.; Auzzas, L.; Casiraghi,
G. J. Org. Chem. 2004, 69, 2611–2613.
4
(
.9. (1S,2S,3R)-1-methyl-cyclopentane-1,2,3-triol (11) and
1S,2R,3R)-1-methyl-cyclopentane-1,2,3-triol (13)
(
2S,5R)-2,5-dihydroxy-2-methyl-cyclopentanone 10 (9.3
mg, 0.071 mmol) was dissolved in MeOH (1 mL). The
obtained solution was treated with NaBH (3.2 mg, 0.086
mmol) at ꢁ5 ꢁC for 1 h, after which acetone (0.1 mL)
was added. The reaction mixture was filtered through
Celite and concentrated. Diastereomers were separated by
flash chromatography (silica gel, DCM/MeOH, 15:1–
1. (a) Comin, M. J.; Leitofuter, J.; Rodriguez, J. B. Tetrahedron
4
2
002, 58, 3129–3136; (b) Bianco, A.; Celona, D.; Di Rita, S.;
Guiso, M.; Melchioni, C.; Umani, F. Eur. J. Org. Chem.
001, 4061–4066; (c) Marco-Contelles, J.; Rodr ´ı guez-Fern a´ n-
2
dez, M. M. Tetrahedron: Asymmetry 1997, 8, 2249–2256; (d)
Ramana, C. V.; Reddy, B. S.; Gurjar, M. K. Tetrahedron
Lett. 2004, 45, 2817–2819.
1
0:1) to yield (1S,2S,3R)-1-methyl-cyclopentane-1,2,3-triol
1
1 (4.9 mg, 0.037 mmol, 52%) and (1S,2R,3R)-1-methyl-
12. Ferrero, M.; Gotor, V. Chem. Rev. 2000, 100, 4319–4347.
1
3. (a) Dauvergne, J.; Happe, A. M.; Jadhav, V.; Justice, D.;
Matos, M.-C.; McCormack, P. J.; Pitts, M. R.; Roberts, S.
M.; Singh, S. K.; Snape, T. J.; Whittall, J. Tetrahedron 2004,
cyclopentane-1,2,3-triol 13 (3.9 mg, 0.030 mmol, 41%).
Compound 11: NMR spectra identical to the data given in
Section 4.8. Compound 13: H NMR (500 MHz, DMSO-
d ): d 1.10 (s, 3H, 1-CH ), 1.42 and 1.72 (m, 2H, H-5), 1.57
and 1.76 (m, 2H, H-4), 3.25 (m, 1H, H-3), 3.88 (bs, 1H, H-
1
6
2
0, 2559–2567; (b) Roy, A.; Schneller, S. W. Tetrahedron Lett.
005, 46, 8913–8915 (and references cited therein); (c) Audran,
6
3
G.; Acherar, S.; Monti, H. Eur. J. Org. Chem. 2003, 92–98.
4. (a) King, S. B.; Ganem, B. J. Am. Chem. Soc. 1991, 113,
5089–5090; (b) Noyori, R.; Tomino, I.; Yamada, M.;
Nishizawa, M. J. Am. Chem. Soc. 1984, 106, 6717–6725.
5. (a) Johnson, C. R.; Barbachyn, M. R. J. Am. Chem. Soc.
1
3
2
), 4.15 (bs, 1H, 1-OH), 4.50 (bs, 2H, 2-OH, 3-OH);
C
1
NMR (125 MHz, DMSO-d ): d 25.92 (1-CH ), 29.61
6
3
(
C-4), 35.70 (C-5), 71.61 (C-3), 76.51 (C-1), 77.46 (C-2).
1
1
984, 106, 2459–2461; (b) Stark, L. M.; Pekari, K.; Sorensen,
Acknowledgments
E. J. Proc. Nat. Acad. Sci. 2004, 101, 12064–12066; (c)
Bisacchi, G. S.; Chao, S. T.; Bachard, C.; Daris, J. P.;
Innaimo, S.; Jacobs, G. A.; Kocy, O.; Lapointe, P.; Martel,
A.; Merchant, Z.; Slusarchyk, W. A.; Sundeen, J. E.; Young,
M. G.; Colonno, R.; Zahler, R. Bioorg. Med. Chem. Lett.
We gratefully acknowledge the support from Competence
Center for Cancer Research, Tallinn, from Estonian Sci-
ence Foundation (Grants Nos. 5628 and 6778) and from
the Estonian Ministry of Education and Research (Grant
1
997, 7, 127–132.
1
6. Paju, A.; Kanger, T.; Pehk, T.; M u¨ u¨ risepp, A.-M.; Lopp, M.
Tetrahedron: Asymmetry 2002, 13, 2439–2448.
0
142725s06).
1
7. (a) Kocienski, P. J. Protecting Groups, 3rd ed.; Georg Thieme
Verlag: Stuttgart, NY, 2004, pp 119–185, and references cited
therein; (b) Green, T.; Wutts, P. G. M. Protective Groups in
Organic Chemistry; John Wiley and Sons, NY, 2004; pp 201–
245, and references cited therein.
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