K. N. Prokhorevich, A. V. Bekish / Tetrahedron Letters 51 (2010) 4073–4075
4075
strated.23 The homochiral forms of the intermediates prepared in
this study are intended to be used for the synthesis of natural
products.
13. Compound 7 was prepared by a standard method using DHP/PPTS/CH2Cl2
starting from commercially available -hydroxy- -butyrolactone. Both
enantiomers of the latter are also commercially available.
14. Compound 8. IR (CCl4) 3586, 3508, 3095 cmÀ1 1H NMR (400 MHz, CDCl3) d
a
c
;
0.39–0.50 (m, 1H), 0.64–0.72 (m, 1H), 0.75–0.88 (m, 2H), 1.49–1.60 (m, 4H),
1.75–2.06 (m, 4H), 2.60 (br s, 2H), 3.42–3.57 (m, 2H), 3.69–3.86 (m, 2H), 3.91–
4.04 (m, 1H), 4.67–4.71 (m, 0.5H), 4.81–4.85 (m, 0.5H). Anal. Calcd for
Acknowledgement
C11H20O4: C, 61.09; H, 9.32. Found: C, 61.04; H, 9.43.
15. The signals of the protons of the methine groups at d = 3.42 ppm for acetonide
9 and d = 4.20 ppm for 10 were used to determine ratio of 9:10.
This work was supported by the Belarusian State University.
References and notes
16. Synthesis of compound 9.
A solution of 2,2-dimethoxypropane (2.90 mL,
23.6 mmol), triol 6 (1.05 g, 8.0 mmol) and PPTS (0.10 g) in acetone (20 mL)
was stirred for 30 min. The reaction was quenched with Et3N (0.5 mL) and the
solvent was removed under reduced pressure. The residue was diluted with
petroleum ether/EtOAc mixture (6/1) and filtered through a small pad of silica
1. Coppola, G. M.; Schuster, H. F. Chiral
a-Hydroxy Acids in Enantioselective
Synthesis; Wiley-VCH: Weinhem, 2002. pp 167–313.
2. For a review, see: (a) Kulinkovich, O. G. Eur. J. Org. Chem. 2004, 22, 4517; For
recent examples, see: (b) Tyvorskii, V. I.; Astashko, D. A.; Kulinkovich, O. G.
Tetrahedron 2004, 60, 1473; (c) Lysenko, I. L.; Kulinkovich, O. G. Zh. Org. Khim.
2005, 41, 73; Russ. J. Org. Chem. (Engl. Trans.) 2005, 41, 70.; (d) Matiushenkov, E.
A.; Kulinkovich, O. G. Zh. Org. Khim. 2006, 42, 509; Russ. J. Org. Chem. (Engl.
Trans.) 2006, 42, 491.; (e) Bekish, A. V.; Prokhorevich, K. N.; Kulinkovich, O. G.
Eur. J. Org. Chem. 2006, 22, 5069; (f) Prokhorevich, K. N.; Kulinkovich, O. G.
Tetrahedron: Asymmetry 2006, 17, 2976; (g) Mineeva, I. V.; Kulinkovich, O. G. Zh.
Org. Khim. 2008, 44, 1277; Russ. J. Org. Chem. (Engl. Trans.) 2008, 44, 1261.; (h)
Astashko, D. A.; Kulinkovich, O. G.; Tyvorskii, V. I. Zh. Org. Khim. 2006, 42, 736;
Russ. J. Org. Chem. (Engl. Trans.) 2006, 42, 714.
3. (a) Bekish, A. V.; Kulinkovich, O. G. Tetrahedron Lett. 2005, 46, 6975; (b) Bekish,
A. V.; Isakov, V. E.; Kulinkovich, O. G. Tetrahedron Lett. 2005, 46, 6979.
4. Dale, J. A.; Dull, D. L.; Mosher, H. S. J. Org. Chem. 1969, 34, 2543.
5. (a) Corey, E. J.; Shirahama, H.; Yamamoto, H.; Terashima, S.; Venkateswarlu, A.;
Schaaf, T. K. J. Am. Chem. Soc. 1971, 93, 1490; (b) Meyers, A. I.; Lawson, J. P.
Tetrahedron Lett. 1982, 23, 4883; (c) Hanessian, S.; Ugolini, A.; Therien, M. J. Org.
Chem. 1983, 48, 4427; (d) Rosen, T.; Taschner, M. J.; Heathcock, C. H. J. Org.
Chem. 1984, 49, 3994; (e) Meyers, A. I.; Lawson, J. P.; Walker, D. G.; Linderman,
R. J. J. Org. Chem. 1986, 51, 5111; (f) Perrier, H.; Huyer, G.; Young, R. N.
Tetrahedron Lett. 1992, 33, 725; (g) Xu, Y.; Qian, L.; Pontsler, A. V.; McIntyre, T.
M.; Prestwich, G. D. Tetrahedron 2004, 60, 43.
gel. Evaporation of the solvent under reduced pressure gave acetonide
9
(1.29 g, 94%). IR (CCl4) 3585, 3092 cmÀ1 1H NMR (400 MHz, CDCl3) d 0.43–0.53
;
(m, 2H), 0.70–0.79 (m, 2H), 1.38 (s, 3H), 1.39 (s, 3H), 1.91–2.02 (m, 2H), 2.97 (br
s, 1H), 3.42 (dd, J = 12.0, 2.5 Hz, 1H), 3.82 (ddd, J = 12.0, 6.0, 2.0 Hz, 1H), 3.82
(td, J = 12.0, 3.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) d 9.6, 12.4, 19.2, 26.3, 29.7,
57.0, 59.5, 73.7, 98.4. Anal. Calcd for C9H16O3: C, 62.77; H, 9.36. Found: C,
62.54; H, 9.21.
17. Synthesis of compound 10.
A solution of 2,2-dimethoxypropane (1.8 mL,
14.6 mmol), triol 6 (0.66 g, 5.0 mmol) and PPTS (0.10 g) in acetone (15 mL)
was stirred at room temperature for 30 min and then heated under reflux for
3 h. The solvent was removed under reduced pressure and the residue was
dissolved in MeOH (15 mL). After standing for 12 h at 5 °C, the reaction was
quenched with Et3N (0.5 mL). The solvent was removed under reduced
pressure. Column chromatography of the residue (8 g of silica gel, eluent:
from petroleum ether/EtOAc 5/1 to EtOAc) gave acetonide 10 (0.49 g, 57%) and
the starting triol 6 (0.15 g, 23%). IR (CCl4) 3639, 3560, 3095 cmÀ1 1H NMR
;
(400 MHz, CDCl3) d 0.54–0.60 (m, 1H), 0.64–0.70 (m, 1H), 0.84–0.91 (m, 1H),
0.97–1.03 (m, 1H), 1.46 (s, 3H), 1.48 (s, 3H), 1.50–1.57 (m, 1H), 1.69–1.78 (m,
1H), 2.41 (br s, 1H), 3.80 (t, J = 5.6 Hz, 2H), 4.20 (dd, J = 9.5, 3.0 Hz, 1H); 13C
NMR (100 MHz, CDCl3) d 6.3, 8.6, 25.9, 27.1, 34.8, 60.4, 64.1, 77.2, 108.3. Anal.
Calcd for C9H16O3: C, 62.77; H, 9.36. Found: C, 62.60; H, 9.27.
18. Chun, S.-K.; Moon, S.-H. J. Chem. Soc., Chem. Commun. 1992, 77.
19. Racemic butane-1,2,4-triol and both enantiomers of the latter are
commercially available.
6. The signals of the protons of the methine groups at d = 3.61 ppm for acetonide
2 and d = 4.32 ppm for 5 were used to determine the ratio of 2:5.
7. Kovalenko, V. N.; Masalov, N. V.; Kulinkovich, O. G. Zh. Org. Chem. 2009, 45,
1333; Russ. J. Chem. (Engl. Trans.) 2009, 45, 1318.
8. Mineyeva, I. V.; Kulinkovich, O. G. Tetrahedron Lett. 2010, 51, 1836.
9. Kitamura, M.; Isobe, M.; Ichikawa, Y.; Goto, T. J. Am. Chem. Soc. 1984, 106, 3252.
10. Corey, E. J.; Kim, S.; Yoo, S.; Nicolaou, K. C.; Melvin, L. S.; Brunelle, D. J.; Falck, J.
R.; Trybulski, E. J.; Lett, R.; Sheldrake, P. W. J. Am. Chem. Soc. 1978, 100, 4620.
20. (a) Thiam, M.; Slassi, A.; Chastrette, F.; Amouroux, R. Synth. Commun. 1992, 22,
83; (b) Tursun, A.; Canet, I.; Aboab, B.; Sinibaldi, M.-E. Tetrahedron Lett. 2005,
46, 2291.
21. The signals of the protons of the methyl groups at d = 1.36 and 1.42 ppm for
acetonide 12 and d = 1.39 and 1.47 ppm for 13 were used to determine ratio of
12:13.
22. Compound 12 was synthesized according to the procedure employed in the
synthesis of acetonide 10.17 Product 12 is slightly volatile. In this connection
removal of the majority of the solvents was performed under atmospheric
pressure using a Vigreux column. A pentane/Et2O mixture (2:1) was used
instead of the petroleum ether/EtOAc system. The spectral data for the
obtained product were identical with those reported in the literature.5
23. We failed to obtain compound 5 in pure form using this methodology due to
11. Synthesis of compound 2.
A solution of 2,2-dimethoxypropane (0.90 ml,
7.3 mmol), triol 4 (0.50 g, 3.2 mmol) and PPTS (0.04 g) in acetone (10 mL)
was stirred at room temperature for 30 min. The reaction was quenched with
Et3N (0.25 mL) and the solvent was removed under reduced pressure. The
residue was diluted with petroleum ether/EtOAc mixture (10:1) and filtered
through a small pad of silica gel. Evaporation of the solvent under reduced
pressure gave acetonide 2 (0.61 g, 97%). Spectral data for compound 2 were
identical to those reported previously.3a
the unfavourable ratio of compounds
2 and 5 in the mixture under
12. Compound 6. IR (neat) 3443 cmÀ1 1H NMR (400 MHz, D2O) d 0.57–0.66 (m,
;
thermodynamic equilibrium conditions (3:1). Moreover, the rate of
deacetalization of acetonide 2 exceeds that of acetonide 5, but not as much
as in the case of compounds 9 and 10.
2H), 0.73–0.81 (m, 2H), 1.81–1.97 (m, 2H), 3.26 (dd, J = 8.8, 4.7 Hz, 1H), 3.69–
3.79 (m, 2H); 13C NMR (100 MHz, D2O) d 11.2, 12.0, 35.3, 57.9, 59.2, 73.9.