2
632
A. T. Khan et al. / Carbohydrate Research 346 (2011) 2629–2632
starting material was complete. The reaction mixture was ex-
tracted with EtOAc (3 ꢂ 25 mL) and the organic layer was washed
with 10% sodium thiosulfate solution to remove excess iodine. Fi-
nally, the organic layer was washed with water and dried over an-
(s, 3H), 1.93 (s, 3H), 1.97 (s, 3H), 4.78–4.88 (m, 2H), 5.07–5.13 (m,
1
3
1H), 5.36 (d, J = 8.0 Hz, 1H), 9.35 (s, 1H); C NMR (100 MHz,
CDCl ): d 16.6, 20.5, 20.7, 20.8, 21.0, 66.8, 67.4, 71.4, 74.3, 170.0,
3
20 9
170.1 (2C), 170.3, 195.5. Anal. Calcd for C14H O (332.30): C,
2 4
hyd Na SO . The solvent was evaporated on rotary evaporator and
50.60; H, 6.07. Found: C, 50.46; H, 6.00.
the crude product was purified by column chromatography using
2
0:80 EtOAc–hexane.
1.2.7. 5-O-Acetyl-2,3,4,6-tetra-O-benzyl-aldehydo-
D
-glucose (21)
ꢁ1 1
Syrup; IR (KBr): 1735 (CO) cm
;
H NMR (400 MHz, CDCl ): d
3
1
.2.1. 2,3,4,5-Tetra-O-acetyl-aldehydo-
D
-ribose (15)
1.90 (s, 3H), 3.62 (dd, J = 4.8 Hz, J = 11.2 Hz, 1H), 3.74 (dd,
J = 3.2 Hz, J = 11.2 Hz, 1H), 3.81–3.85 (m, 2H), 3.95–3.97 (m, 1H),
4.30–4.44 (m, 7H), 4.71 (d, J = 11.6 Hz, 1H), 5.11 (d, J = 3.2 Hz,
6
25
White solid; mp 96–97 °C (lit 93–94 °C); ½
a
ꢃ
ꢁ12.4 (c 1.0,
): d
.0 (s, 3H), 2.05 (s, 3H), 2.08 (s, 3H), 2.18 (s, 3H), 4.15 (dd,
J = 4.4 Hz, J = 12.8 Hz, 1H), 4.34 (dd, J = 2.0 Hz, J = 8.4 Hz, 1H),
.26–5.31 (m, 1H), 5.44 (d, J = 2.0 Hz, 1H), 5.60 (dd, J = 2.4 Hz,
D
MeOH); IR (KBr): 1748 (CO) cm 1; H NMR (400 MHz, CDCl
ꢁ
1
3
1
3
2
3
1H), 7.07–7.23 (m, 20H), 9.59 (s, 1H); C NMR (100 MHz, CDCl ):
d 21.2, 68.1, 72.5, 73.1, 73.2, 73.7, 74.0, 76.7, 79.7, 80.3, 127.7 (2C),
127.9 (2C), 128.1 (2C), 128.2 (2C), 128.3 (2C), 128.4 (3C), 128.43
(3C), 128.5 (4C), 137.1, 137.2, 137.6, 137.8, 170.0, 200.1. Anal.
5
13
J = 9.2 Hz, 1H), 9.53 (s, 1H); C NMR (100 MHz, CDCl
0.7 (3C), 61.4, 68.3, 68.4, 76.7, 169.1, 169.5, 169.8, 170.6, 193.2.
Anal. Calcd for C13 (318.28): C, 49.06; H, 5.70. Found: C,
3
): d 20.4,
2
Calcd for C36
H, 6.48.
38 7
H O (582.68): C, 74.21; H, 6.57. Found: C, 74.09;
18 9
H O
4
8.93; H, 5.61.
1
.2.8. 2,3:4,5-Di-O-isopropylidene-aldehydo-L-arabinose (22)
2
5
ꢁ1
1
.2.2. 2,3,4,5-Tetra-O-acetyl-aldehydo-
L
-arabinose (16)
ꢁ60.0 (c 2.0, CHCl ); IR (KBr):
): d 2.07 (s, 3H), 2.07 (s,
H), 2.07 (s, 3H), 2.08 (s, 3H), 4.16–4.20 (m, 1H), 4.31 (dd,
Syrup; ½
a
ꢃ
+10 (c 0.25, CH
2 2
Cl ); IR (KBr): 1739 (CO) cm ;
D
25
1
White solid; mp 115–116 °C; ½
aꢃ
3
H NMR (400 MHz, CDCl
3
): d 1.33 (s, 3H), 1.36 (s, 3H), 1.40 (s,
D
ꢁ
1 1
1
3
749 (CO) cm ; H NMR (400 MHz, CDCl
3
3H), 1.45 (s, 3H), 3.94–4.15 (m, 4H), 4.39 (dd, J = 0.8 Hz,
1
3
J = 6.0 Hz, 1H), 9.73 (s, 1H); C NMR (100 MHz, CDCl
3
): d 25.3,
J = 2.4 Hz, J = 12.4 Hz, 1H), 5.24–5.28 (m, 1H), 5.38 (d, J = 2.0 Hz,
H), 5.68 (dd, J = 2.4 Hz, J = 9.2 Hz, 1H), 9.73 (s, 1H); 13C NMR
100 MHz, CDCl ): d 20.5, 20.7, 20.9 (2C), 61.7, 67.4, 68.2, 76.1,
69.8, 169.9, 170.9 (2C), 194.1. Anal. Calcd for C13 (318.28):
26.4, 26.9, 27.2, 67.2, 76.65, 77.9, 83.5, 110.2, 112.1, 200.1. Anal.
1
(
1
Calcd for C11
H, 7.97.
18 5
H O (230.26): C, 57.38; H, 7.88. Found: C, 57.51;
3
18 9
H O
C, 49.06; H, 5.70. Found: C, 48.94; H, 5.61.
Acknowledgments
1
.2.3. 2,3,4,5,6-Penta-O-acetyl-aldehydo-
D
-glucose (17)
S.A. and M.M.K. are thankful to the UGC, New Delhi, India for
their research fellowship. Similarly, R.S.B. and M.L. are grateful to
CSIR, New Delhi, India for their financial assistance. The authors
are grateful to the Director, IIT Guwahati, for providing the general
facilities to carry out this work. We are also thankful to the referees
for their valuable comments and suggestions.
6
25
White solid; mp 118–119 °C (lit 116–117 °C), ½
a
ꢃ
+4.2 (c 2.0,
D
ꢁ1
1
3 3
CHCl ); IR (KBr): 1749 (CO) cm ; H NMR (400 MHz, CDCl ): d
2
.04 (s, 9H), 2.10 (s, 3H), 2.18 (s, 3H), 4.07 (dd, J = 5.2 Hz,
J = 12.4 Hz, 1H), 4.25 (dd, J = 2.8 Hz, J = 12.8 Hz, 1H), 5.08–5.13
m, 1H), 5.25 (d, J = 5.2 Hz, 1H), 5.48 (dd, J = 3.6 Hz, J = 7.6 Hz,
H), 5.57 (dd, J = 3.6 Hz, J = 4.8 Hz, 1H), 9.50 (s, 1H); 13C NMR
100 MHz, CDCl ): d 20.4, 20.5, 20.6, 20.77, 20.83, 61.8, 68.3,
8.4, 68.6, 75.2, 169.4, 169.6, 169.8, 169.9, 170.7, 194.0. Anal. Calcd
11 (390.34): C, 49.23; H, 5.68. Found: C, 49.11; H, 5.60.
(
1
(
6
3
References
1.
2.
3.
Khan, A. T.; Sharma, P.; Schmidt, R. R. J. Carbohydr. Chem. 1995, 14, 1353–1367.
Khan, A. T.; Ahmed, W.; Schmidt, R. R. Carbohydr. Res. 1996, 280, 277–286.
Chang, Y. K.; Lee, B. Y.; Kim, D. J.; Lee, G. S.; Jeon, H. B.; Kim, K. S. J. Org. Chem.
2005, 70, 3299–3302.
22
for C16H O
1
.2.4. 2,3,4,5,6-Penta-O-acetyl-aldehydo-D-galactose (18)
6
25
D
4. Pattenden, G.; González, M. A.; Little, P. B.; Millan, D. S.; Plowright, A. T.;
Tornos, J. A.; Ye, T. Org. Biomol. Chem. 2003, 1, 4173–4208.
5. Sun, J.; Han, X.; Yu, B. Org. Lett. 2005, 7, 1935–1938.
White solid; mp 105–110 °C (lit 106–110 °C), ½
a
ꢃ
ꢁ6.0 (c 2.0,
ꢁ
1
1
3 3
CHCl ); IR (KBr): 1750 (CO) cm ; H NMR (400 MHz, CDCl ): d
2
3
.04 (s, 3H), 2.05 (s, 3H), 2.11 (s, 3H), 2.12 (s, 3H), 2.22 (s, 3H),
.90 (dd, J = 3.6 Hz, J = 11.2 Hz, 1H), 4.28 (dd, J = 5.2 Hz,
6. Roberts, J. C.; Nagasawa, H. T.; Zera, R. T.; Fricke, R. F.; Goon, D. J. W. J. Med.
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7
8
.
.
Wolfrom, M. L. J. Am. Chem. Soc. 1929, 51, 2188–2193.
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J = 11.6 Hz, 1H), 5.29 (d, J = 15.6 Hz, 1H), 5.37 (t, J = 5.6 Hz, 1H),
5
NMR (100 MHz, CDCl
1
3
.47 (d, J = 10.0 Hz, 1H), 5.65 (d, J = 9.6 Hz, 1H), 9.46 (s, 1H);
C
4383.
): d 20.6, 20.8 (4C), 62.1, 66.4, 67.7 (2C),
9. Tang, C. J.; Wu, Y. Tetrahedron 2007, 63, 4887–4906.
3
1
0. Sambaiah, T.; Fanwick, P. E.; Cushman, M. J. Org. Chem. 2001, 66, 4405–4408.
1. Eitelman, S. J.; Horton, D. Carbohydr. Res. 2006, 341, 2658–2668.
2. Ohlsson, J.; Magnusson, G. Carbohydr. Res. 2001, 331, 91–94.
3. Lichtenthaler, F. W.; Lorenz, K.; Ma, W. Y. Tetrahedron Lett. 1987, 28, 47–50.
4. Khan, A. T.; Mondal, E.; Sahu, P. R. Synlett 2003, 377–381.
7
5.9, 170.3, 170.5, 170.8 (3C), 193.9. Anal. Calcd for C16
22 11
H O
1
1
1
1
1
(
390.34): C, 49.23; H, 5.68. Found: C, 49.09; H, 5.58.
1
.2.5. 2,3,4,5,6-Penta-O-acetyl-aldehydo-
D
-mannose (19)
); IR (KBr): 1749 (CO) cm ; H
): d 2.05 (s, 3H), 2.06 (s, 3H), 2.09 (s, 3H),
.11 (s, 3H), 2.17 (s, 3H), 4.09–4.14 (m, 1H), 4.21 (dd, J = 2.8 Hz,
J = 10.0 Hz, 1H), 5.03 (dd, J = 0.8 Hz, J = 7.6 Hz, 1H), 5.12–5.17 (m,
H), 5.45–5.50 (m, 2H), 9.41 (s, 1H); 13C NMR (100 MHz, CDCl
):
d 20.4, 20.5, 20.6, 20.7, 20.8, 61.8, 67.4, 67.6, 67.8, 74.3, 169.66,
69.7, 169.8, 170.0, 170.6, 195.4. Anal. Calcd for C16
390.34): C, 49.23; H, 5.68. Found: C, 49.33; H, 5.74.
5. Mondal, E.; Bose, G.; Khan, A. T. Synlett 2001, 785–786.
2
5
ꢁ1 1
Syrup; ½
aꢃ
D
2 2
+23.6 (c 1.0, CH Cl
16. Mandal, P. K.; Mishra, A. K. Synlett 2007, 1207–1210.
17. Mondal, E.; Bose, G.; Sahu, P. R.; Khan, A. T. Chem. Lett. 2001, 11, 1158–1159.
NMR (400 MHz, CDCl
2
3
1
1
8. Khan, A. T.; Boruwa, J.; Mondal, E.; Bose, G. Indian J. Chem., Sect. B 2001, 40,
039–1042.
9. Khan, A. T.; Goswami, P.; Choudhury, L. H. Tetrahedron Lett. 2006, 47, 2751–
2754.
1
1
3
20. Khan, A. T.; Goswami, P. Tetrahedron Lett. 2005, 46, 4937–4940.
21. Barua, P. M. B.; Sahu, P. R.; Mondal, E.; Bose, G.; Khan, A. T. Synlett 2002, 81–84.
22. Shotwell, J. B.; Krygowski, E. S.; Hines, J.; Koh, B.; Huntsman, E. W. D.; Choi, H.
W., ; Schneekloth, J. S., Jr.; Wood, J. L.; Crews, C. M. Org. Lett. 2002, 4, 3087–
1
(
22 11
H O
3089.
2
2
3. Blanc, A.; Toste, F. D. Angew. Chem., Int. Ed. 2006, 45, 2096–2099.
4. Kantam, M. L.; Neelam, B.; Reddy, C. V.; Chaudhuri, M. K.; Dehury, S. K. Catal.
Lett. 2006, 95, 19–22.
1
.2.6. 2,3,4,5-Tetra-O-acetyl-aldehydo-
L
-rhamnose (20)
); IR (KBr): 1748 (CO) cm ; H
): d 1.04 (d, J = 6.4 Hz, 3H), 1.87 (s, 3H), 1.91
2
5
ꢁ1 1
Syrup; ½
aꢃ
ꢁ33 (c 0.06, CH
2 2
Cl
D
NMR (400 MHz, CDCl
3
25. Khan, A. T.; Khan, M. M. Carbohydr. Res. 2010, 345, 2139–2145.