A. Murugan et al. / Tetrahedron Letters 46 (2005) 6235–6238
6237
Me
Me
OMOM
OMOM
OMOM
a
b
7
+
HO
HO
HO
O
O
O
O
O
O
12
13
14
c
3
Scheme 4. Reagents and conditions: (a) (i) 1,10-thiocarbonyldiimidazole, toluene, reflux, 6 h; (ii) trimethyl phosphite, reflux, 9 h, (85%) from (7); (b)
Pd/C–H2, MeOH, 8 h, 40 psi, 97%; (c) cat. HCl, MeOH, rt, 10 h, 95%.
3. Maras, A.; Secen, H.; Sutbeyaz, Y.; Balci, M. J. Org.
¨
in MeOH gave (ꢀ)-gala quercitol 2 in excellent yield,
with analytical data in agreement with reported values.13
Chem. 1998, 63, 2039–2041, and references cited therein.
4. McCasland, G. E.; Naumann, M. O.; Durham, L. J. J.
Org. Chem. 1968, 33, 4220–4227.
We next turned our attention to the synthesis of 3 from
7. The triol 7 was converted in to the exo-olefin 12 by
employing the Corey–Winter protocol.14 We anticipated
that reduction of the exo-olefin would proceed in a man-
ner similar to the carbonyl reduction. Catalytic hydroge-
nation of 12 with 10% Pd/C at 40 psi in methanol
afforded a diastereomeric mixture of 1315 and 14 in a
ratio of 93:7, which were separated by flash column
chromatography. All attempts to improve the selectiv-
ity, including changing the catalyst were unsuccessful.
Global deprotection of 13 with cat. HCl in methanol
gave 3 in excellent yield with analytical data in agree-
ment with the literature values7a,16 (Scheme 4).
5. For reviews, see: (a) Suami, T. Pure Appl. Chem. 1987, 59,
1509–1520; (b) Suami, T.; Ogawa, S. Adv. Carbohydr.
Chem. Biochem. 1990, 48, 21–90; (c) Suami, T. Top. Curr.
Chem. 1990, 154, 257–283.
6. Berecibar, A.; Grandjean, C.; Sinwardena, A. Chem. Rev.
1999, 99, 779–844.
7. (a) Redlich, H.; Sudau, W.; Szadenings, A. K.; Vollerthun,
R. Carbohydr. Res. 1992, 226, 57–78; (b) Valsecchi, E.;
Tacchi, A.; Prosperi, D.; Compostella, F.; Panza, L.
Synlett 2004, 2529–2532.
8. Ulibarri, G.; Nadler, W.; Skrydstrup, T.; Audrain, H.;
Chiaroni, A.; Riche, C.; Grierson, D. S. J. Org. Chem.
1995, 60, 2753–2761.
9. Compound 9: White solid. Mp 97 °C. 1H NMR (200 MHz,
CDCl3): d 4.83 (s, 2H), 4.26 (dd, J = 5.0, 3.7 Hz, 1H), 4.15
(m, 2H), 3.84 (ddd, J = 14.1, 9.2, 4.9 Hz, 1H), 3.62 (br s,
1H), 3.45 (br s, 4H), 2.05 (dt, J = 14.1, 5.1 Hz, 1H), 1.87
(ddd, J = 13.2, 9.5, 3.7 Hz, 1H), 1.75–1.50 (m, 8H), 1.41
(m, 2H). 13C NMR (50 MHz, CDCl3): d 97.6, 86.0, 78.2,
77.7, 66.7, 66.5, 55.8, 37.8, 35.1, 34.6, 24.9, 23.9, 23.6. Anal.
Calcd for C14H22O6: C, 58.32; H, 8.39. Found: C, 58.04; H,
In conclusion, we have successfully synthesized (+)-pro-
to, (ꢀ)-gala quercitols and carba-L-rhamnose from D-
(ꢀ)-quinic acid in ten linear steps.
Acknowledgements
25
8.51. ½aꢁD ꢀ12.6 (c 0.70, CHCl3).
10. Compound 11: Clear syrup. 1H NMR (500 MHz, CDCl3):
d 8.07 (m, 4H), 7.57 (dd, J = 7.6, 6.4 Hz, 2H), 7.45 (m, 4H),
5.69 (m, 1H), 5.46 (ddd, J = 12.6, 8.9, 3.7 Hz, 1H), 4.89 (d,
J = 6.6 Hz, 1H), 4.79 (d, J = 6.6 Hz, 1H), 4.35 (t, J =
5.7 Hz, 1H), 4.33 (t, J = 4.2 Hz, 1H), 4.11 (dd, J = 8.3,
5.7 Hz, 1H), 3.33 (s, 3H), 2.29 (dt, J = 14.0, 5.5 Hz, 1H),
2.22 (ddd, J = 14.0, 12.6, 3.7 Hz, 1H), 1.85 (t, J = 6.2 Hz,
2H), 1.7–1.55 (m, 6H), 1.4 (m, 2H). 13C NMR (50 MHz,
CDCl3): d 165.6, 165.3, 133.3, 133.1, 129.9, 129.8, 129.7,
128.5, 128.4, 110.5, 96.5, 78.5, 77.0, 75.3, 70.0, 69.4, 55.8,
A.K.Y. thanks CSIR for financial assistance in the form
of a fellowship.
Supplementary data
Supplementary data associated with this article can be
25
37.9, 35.4, 30.0, 24.9, 23.9, 23.7. ½aꢁD +45 (c 0.2, CHCl3).
11. Salamci, E.; Secen, H.; Sutbeyaz, Y.; Balci, M. J. Org.
¨
25
Chem. 1997, 62, 2453–2457, Optical rotation: ½aꢁD +25.1
(c 0.5, H2O). Lit.2 +26 (H2O).
References and notes
12. Compound 10: Clear syrup. 1H NMR (200 MHz, CDCl3):
d 4.80 (dd, J = 16.8. 6.6 Hz, 2H), 4.30 (m, 2H), 4.40 (br s,
1H), 4.10 (m, 1H), 3.75 (d, J = 8.9 Hz, 1H), 3.70 (dd,
J = 5.9, 2.8 Hz, 1H), 3.40 (s, 3H), 2.95 (br s, 1H), 2.18 (dt,
J = 14.9, 4.6 Hz, 1H), 1.92 (dt, J = 14.9, 3.3 Hz, 1H),
1.75–1.50 (m, 8H), 1.40 (m, 2H). 13C NMR (50 MHz,
CDCl3): d 109.7, 95.7, 78.6, 78.4, 75.6, 69.4, 67.9, 55.6,
38.0, 35.4, 31.3, 24.9, 23.9, 23.6. Anal. Calcd for
C14H24O6: C, 58.32: H, 8.39. Found: C, 59.16; H, 8.56.
1. (a) Hudlicky, T.; Entwistle, D. A.; Pitzer, K. K.; Thorpe,
A. J. Chem. Rev. 1996, 96, 1195–1220; (b) Kiddle, J. J.
Chem. Rev. 1995, 95, 2189–2202; (c) Hudlicky, T.;
Cebulak, M. Cyclitols and Derivatives; VCH: New York,
1993; (d) Billington, D. C. The Inositol Phosphates-
Chemical Synthesis and Biological Significance; VCH:
Weinheim, 1993.
2. McCasland, G. E.; Furuta, S.; Johnson, L. F.; Shoolery, J.
N. J. Am. Chem. Soc. 1961, 83, 2335–2343.
25
½aꢁD +32.9 (c 1.5, CHCl3).