Vol. 22, No. 1, 2011
Riatto et al.
175
with MeOH (3 mL) with intense formation of bubbles,
and stirred for 1 h. The solvent was distilled off and the
residue purified by column chromatography on silica gel
(elution with AcOEt:hexane 4:1 to MeOH/AcOEt 1:19)
to afford methyl 3,5-dihydroxy pentanoate (135.9 mg,
80%) as a colorless oil (Rf = 0.3 with AcOEt as eluent).
IR nmax/cm-1: 3452, 1738, 1435, 1288, 1171, 1108, 1011;
1H NMR (300 MHz; CDCl3) d 4.23 (quint, J 6.3 Hz, 1H),
3.97 (b, 1H), 3.77 (q, J 6.5 Hz, 2H), 3.67 (s, 3H), 2.90 (b,
1H), 2.48 (d, J 6.2 Hz, 2H), 1.68 (q, J 6.0 Hz, 2H); 13C NMR
(75 MHz; CDCl3) d 173.0, 67.2, 60.3, 51.8, 41.4, 37.8.
Literature (Kingston et al.2): 1H NMR (400 MHz, CDCl3)
d 4.20 (m, 1H), 3.90 (br, 1H), 3.75 (m, 2H), 3.65 (s, 3H),
3.40 (br, 1H), 2.46 (dd, J 5.8 and 1.2 Hz, 2H), 1.65 (q, J
5.6 Hz, 2H); 13C NMR (100 MHz, CDCl3) d 173.2, 67.4,
60.5, 51.9, 41.7, 38.1.
2. For examples of syntheses employing 2, see: Mitton-Fry, M. J.;
Cullen A. J.; Sammakia, T.; Angew. Chem., Int. Ed. 2007, 46,
1066; McAllister, L.A.; Hixon, M. S.; Schwartz, R.; Kubitz, D.
S.; Janda, K. D.; Bioconjugate Chem. 2007, 18, 559. Employing
3, see: Chen, K. H.; Ganesh, T.; Brodie, P.; Slebodnick, C.;
Jiang,Y.; Banerjee, A.; Bane, S.; Snyder, J. P.; Kingston, D. G.
I.; Org. Biomol. Chem. 2008, 6, 4542. Employing 4, see: Sax,
M.; Fröhlich, R.; Schepmann, D.; Wünsch, B.; Eur. J. Org.
Chem. 2008, 6015; Hollenstein M.; Leumann, C. J.; Org. Lett.
2003, 5, 1987; Wender, P. A.; Baryza, J. L.; Bennett, C. E.;
Bi, F. C.; Brenner, S. E.; Clarke, M. O.; Horan, J. C.; Kan, C.;
Lacôte, E.; Lippa, B.; Nell, P. G.; Turner, T. M.; J. Am. Chem.
Soc. 2002, 124, 13648.
3. Dimethyl 3-oxoglutarate: U$ 30.00/25g or U$ 82.80/100g;
dimethyl 3-hydroxyglutarate: U$ 222.00/25g. Source: Aldrich
Chemistry Catalog 2009-2010.
4. Cappuyns, L.; Bull. Soc. Chim. Bel. 1945, 54, 73; Lochte, H.
L.; Pickard, P. L.; J. Am. Chem. Soc. 1946, 68, 721; Paul, R.;
Tchelitcheff, S.; Bull. Soc. Chim. Fr. 1951, 18, 550; Grundmann
C.; Paul, H.; Chem. Ber. 1953, 86, 186; Stetter, H.; Bander, O.
E.; Neumann, W.; Chem. Ber. 1956, 89, 1922.
Synthesis of 1,3,5-pentanetriol (4)
To a stirred solution of dimethyl 3-oxoglutarate (200mg,
1.15 mmol) in THF (3.5 mL) under argon at 45-50 °C was
•
added BH3 Me2S (3 equiv., 332 mL, 3.45 mmol) drop to
5. Lam, L. K. P.; Jones, J. B.; Can. J. Chem. 1988, 66, 1422. A
good yield but tedious aqueous procedure is also described: Roy,
R.; Rey, A. W.; Synlett 1990, 448; Cohen, S. G.; Khedouri, E.;
J. Am. Chem. Soc. 1961, 83, 4228.
drop. After 48 h the reaction was diluted with MeOH (3.5
mL) with intense formation of bubbles, and stirred for
1 h. The solvent was distilled off and the residue purified
by column chromatography on silica gel (elution with
AcOEt to MeOH:AcOEt 1:9) to provide 1,3,5-pentanetriol
(135.2 mg, 98%) as a viscous oil (Rf = 0.1 with AcOEt
as eluent). IR nmax/cm-1: 3348, 2944, 2888, 1422,
6. Mori, K.; Ikunaka, M.; Tetrahedron 1987, 43, 45.
7. Acevedo, C. M.; Kogut, E. F.; Lipton, M.A.; Tetrahedron 2001,
57, 6353.
8. Saito, S.; Hasegawa, T.; Inaba, M.; Nishida, R.; Fujii, T.;
Nomizu, S.; Moriwake, T.; Chem. Lett. 1984, 1389.
9. Thiam, M.; Slassi, A.; Chastrette, F.; Amouroux, R.; Synth.
Commun. 1992, 22, 83. See also Kingston et al.2.
1
1062; H NMR (300 MHz; CD3COCD3) d 4.05-3.92 (m,
2H), 3.80-3.65 (m, 4H), 2.98 (m, 2H), 1.70-1.50 (m, 4H);
13C NMR (75 MHz; CD3COCD3) d 69.2, 60.5, 40.7.
Literature (Wender et al. at reference 2): IR nmax/cm-1:
3338, 2944, 2888, 1421, 1061; 1H NMR (500 MHz; D2O)
d 3.82 (m, J 4.0 Hz, 1H), 3.64 (s, J 6.5 Hz, 4H), 1.66 (m,
4H); 13C NMR (125 MHz; CD3OD) d 67.4, 60.1, 41.1.
10. Loubinoux, B.; Sinnes, J. L.; O´Sullivan, A. C.; Winkler, T.;
Tetrahedron 1995, 51, 3549.
11. Prepared by treatment of anion of ethyl acetoacetate with benzyl
chloromethyl ether: Taylor, E. C.; LaMattina, J. L.; J. Org.
Chem. 1978, 43, 1200.
Acknowledgments
12. Miyashita, M.; Suzuki, T.; Hoshino, M.; Yoshikoshi, A.;
Tetrahedron 1997, 53, 12469.
Financial support from Centro Universitário FIB
(fellowship to V. B. C.) is gratefully acknowledged. We
thank Dr. S. D. Cunha, Dr. J. M. David and Dr. R. A. Pilli
for support.
13. Brown, H. C.; Krishnamurthy, S.; Tetrahedron 1979, 35, 567.
14. Adkins, H.; Billica, H. R.; J. Am. Chem. Soc. 1948, 70, 3121.
15. Viscontini, M.; Ebnother, C.; Helv. Chim. Acta 1951, 34,
116; Jacobs, M. F.; Suthers, B. D.; Hübener A.; Kitching, W.;
J. Chem. Soc., Perkin Trans. I 1995, 901.A non-direct four steps
synthesis is described in high yields, but without experimental
details. See reference 6.
References
1. Seyden-Penne, J. In Reductions by the Alumino and
Borohydrides in Organic Synthesis; Curran, D. P. ed.; 2nd ed.;
Wiley-VCH: New York, 1997; Hudlikly, M. In Reductions in
Organic Chemistry; 2nd ed.; John Wiley & Sons: New York,
1984.
16. Reagent is 1,6-heptadien-4-ol: U$ 356.00/25g. See Wender
et al.2.
Submitted: May 25, 2010
Published online: July 29, 2010