B. Das, D. N. Kumar / Tetrahedron Letters 51 (2010) 6011–6013
6013
OH
O
OH
HO
OH
OH
O
BnO
BnO
OH
OEt
O
OPh
OPh
9
OH
1
8
OBn
Br
HO
10
11
12
OH
HO
Scheme 4. Alternative retrosynthetic analysis of 2,5-anhydro
D
-glucitol 1.
O
O
BnO
a
BnO
OEt
b
BnO
OH
OH
O
13
10
14
OH
O
O
O
c
d
BnO
BnO
OEt
OPh
OH
15
9
PhO
OH
OH
OH
O
e
f
BnO
BnO
OH
O
OPh
OPh
16
BnO
OH
8
17
HO
OH
g
O
HO
OH
1
Scheme 5. Alternative synthesis of 2,5-anhydro
ee 97%; (b) (i) IBX, DMSO, CH2Cl2, 0 °C to rt, 3 h; (ii) PPh3CHCOOEt, CH2Cl2, rt, 2 h, 82% (in two steps); (c) [Pd(PPh3)4], pinacol, B(OPh)3, THF, rt, 30 min, 89%; (d) DIBAL-H,
CH2Cl2, À78 °C, 3 h, 83%; (e) Ti(iOPr)4, (+)-DET, TBHP, CH2Cl2, À20 °C, 78%, ee 96%; (f) CSA, CH2Cl2, 0 °C, 20 min, 72%; (g) ammonium formate, Pd/C, MeOH, reflux, 4 h, 67%.
D
-glucitol 1. Reagents and conditions: (a) Ti(iOPr)4 (0.2 equiv), (+)-DIPT (0.3 equiv), TBHP (2.5 equiv), CH2Cl2, À20 °C, 4 h, 93%,
2. (a) Cardillo, G.; Orena, M. Tetrahedron 1990, 46, 3321; (b) Harmage, J. C.;
The THF derivative 7 was formed from the epoxy alcohol
derived from 2 (Scheme 3) and the other related compound 17
Figadere, B. Tetrahedron: Asymmetry 1993, 4, 1711; (c) Koert, U. Synthesis 1995,
115; (d) Chakraborty, T. K.; Jayaprakash, S.; Diwan, P. V.; Nagaraj, R.; Jampani,
S. R. B.; Kunwar, A. C. J. Am. Chem. Soc. 1998, 120, 12962; (e) Miura, K.; Hosomi,
A. Synlett 2003, 143; (f) Wolfe, J. P.; Hay, M. B. Tetrahedron 2007, 63, 261; (g)
Donohoe, T. J.; Williams, O.; Churchill, G. H. Angew. Chem., Int. Ed. 2008, 47,
2869; (h) Friestad, G. K.; Lee, H. J. Org. Lett. 2009, 11, 3958.
from 8 (Scheme 5) by 5-endo-tet cyclization. The epoxide ring in
each compound (2 or 8) is in -orientation. It is activated by the
a
Lewis or protic acid and the hydroxyl nucleophile at C-5 attacks
the C-2 position from the opposite direction of the epoxide ring
to open it. Thus the cyclization takes place resulting in the
formation of a THF derivative with the inversion of configuration
at C-2 without disturbing the remaining stereogenic centers.
In conclusion, we have developed a highly stereoselective
synthesis of tetrasubstituted tetrahydrofurans following two
approaches starting from a chiral or a non-chiral molecule by
applying intramolecular 5-endo-tet cyclization of 2,3-epoxy
alcohols involving hydroxyl nucleophile. This synthetic method is
a useful example of the 5-endo-tet mode of cyclization. In our
approach the syn-opening of the epoxide ring has been accom-
plished to generate the required 2,3-epoxy alcohol.
3. (a) Aurodox-Maehr, H.; Leach, M.; Williams, T. H.; Benz, W.; Blount, J. F. J. Am.
Chem. Soc. 1973, 95, 8448; (b) Dewey, R. S.; Arison, B. H.; Hannah, J.; Shih, D. H.;
Albers-Schonberg, G. J. Antibiot. 1985, 38, 1691.
4. (a) Dolle, R. E.; Nicolaou, K. C. J. Am. Chem. Soc. 1985, 107, 1691; (b) Dolle, R. E.;
Nicolaou, K. C. J. Am. Chem. Soc. 1985, 107, 1693.
5. (a) Baldwin, J. E. Chem. Commun. 1976, 734; (b) Baldwin, J. E.; Cutting, J.;
Dupont, W.; Kruse, L.; Silberman, L.; Thomas, R. C. Chem. Commun. 1976, 736;
(c) Baldwin, J. E.; Thomas, R. C.; Kruse, L. I.; Silberman, L. J. Org. Chem. 1977, 42,
3846.
6. (a) Karikomi, M.; Watanabe, S.; Kimura, Y.; Uyehara, T. Tetrahedron Lett. 2002,
43, 1495; (b) Doan, H. D.; Gallon, J.; Piou, A.; Vatele, J.-M. Synlett 2007, 983; (c)
Kang, B.; Mowat, J.; Pinter, T.; Britton, R. Org. Lett. 2009, 11, 1717.
7. (a) Persky, R.; Albeck, A. J. Org. Chem. 2000, 65, 5632; (b) Bennek, J. A.; Gray, G.
R. J. Org. Chem. 2002, 67, 8862; (c) Donohoe, T.; Butterworth, S. Angew. Chem.,
Int. Ed. 2003, 42, 8.
8. (a) Hungerbuhelr, E.; Seebach, D. Helv. Chim. Acta 1984, 64, 687; (b) Seyforth,
D.; Vaughau, L. G. J. Organomet. Chem. 1963, 1, 138.
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5421.
References and notes
10. (a) Cookson, R. C.; Wallis, S. R. J. Chem. Soc. B 1966, 1245; (b) Poulard, C.; Carnet,
J.; Legoupy, S.; Dujardiu, G.; Dhal, R.; Huct, F. Lett. Org. Chem. 2009, 6, 359.
11. Yu, X. Q.; Yoshimura, F.; Ito, F.; Sasaki, M.; Hirai, A.; Tanino, K.; Miyashita, M.
Angew. Chem., Int. Ed. 2008, 47, 750.
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