Stereoselective Synthesis of New Higher Carbon Sugars from D-Xylose
SHORT COMMUNICATION
3
1 H, 5Ј-H), 2.21 (m, 3 H, 5-H, 6-H and 6Ј-H), 4.12 (d, J
ϭ
From the structures of compounds 4 and 5, it could be
seen that compound 3 has a double bond between C7 and
C8 and a carbonyl group on C3. This confirms that com-
pound 3 is formed by two molecules of compound 2
through a hetero-DielsϪAlder reaction, as shown in
Scheme 2.
H,H
5.6 Hz, 1 H, 3-H), 4.87 (dd, 3J H,H ϭ 5.6, 3J H,H ϭ 4.0 Hz, 1 H, 2-
3
H), 5.16 (m, 1 H, 9-H), 5.80 (d, JH,H ϭ 3.6 Hz, 1 H, 1-H), 5.92
(d, J
ϭ 5.2 Hz, 1 H, 10-H) ppm. 13C NMR (100 MHz, [D6]-
3
H,H
acetone, 25 °C, TMS): δ ϭ 18.1 (C-6), 26.0 (C-5), 27.2 (CH3), 27.3
(CH3), 27.7 (CH3), 28.0 (CH3), 74.8 (C-3), 81.1 (C-2), 81.3 (C-9),
104.4 (C-1), 105.2 (C-10), 109.7 (C-4), 112.5 (C-11), 115.3 (C-14),
130.8 (C-8), 137.9 (C-7) ppm. HRMS: m/z calcd. for C16H22O8 [M]:
342.1315, found 342.1341. C16H22O8 (342.34): calcd. C 56.13, H
6.48; found C 56.01, H 6.67.
Conclusion
Compound 5: A solution of 4 (1 g, 2.9 mmol) in ethanol (60 mL)
was hydrogenated (3 bars) for 3 h in the presence of 5% Pd/C (1 g).
The reaction mixture was filtered through a short silica-gel column
and the solvents evaporated. The residue was crystallized from
ethanol to yield the product as colorless needles (0.9 g, 90%). M.p.
180Ϫ182 °C. IR (KBr): ν˜ ϭ 3534 cmϪ1 (OH). 1H NMR (400 MHz,
[D6]acetone, 25 °C, TMS): δ ϭ 1.33 (s, 3 H, CH3), 1.39 (s, 3 H,
CH3), 1.52 (s, 3 H, CH3), 1.56 (s, 3 H, CH3), 2.05Ϫ1.83 (m, 4 H,
In conclusion, we have developed a facile one-pot ap-
proach for the synthesis of the C10 higher carbon sugars
under mild conditions with reasonable yields. The higher
carbon sugars can be synthesized from -xylose on a large
scale both conveniently and economically. The higher car-
bon monosaccharides can be used in the synthesis of higher
carbon amino sugars and glycosidase inhibitors, as well as
new nucleosides with two anomeric carbons. Studies
towards the synthesis of glycosidase inhibitors and new nu-
cleoside are underway in our laboratory.
3
3
5-H and 6-H), 3.86 (dd, J
ϭ 3.6, J
ϭ 8.0 Hz, 1 H, 7-H),
H,H
H,H
4.06 (dd, 3J
ϭ 3.6, 3J
ϭ 5.6 Hz, 1 H, 8-H), 4.16 (d, 3J
H,H
H,H
3
3
ϭ 5.6 Hz, 1 H, 3-H), 4.78 (dd, J
ϭ 4.8, J
ϭ 5.6 Hz,
H,H
H,H
H,H
1 H, 9-H), 4.84 (dd, 3J H,H ϭ 4.0, 3J H,H ϭ 5.6 Hz, 1 H, 2-H), 5.67
3
3
(d, J H,H ϭ 4.8 Hz, 1 H, 10-H), 5.88 (d, J H,H ϭ 4 Hz, 1 H, 1-H)
ppm. 13C NMR (100 MHz, [D6]acetone, 25 °C, TMS): δ ϭ 23.5
(C-6), 24.2 (C-5), 27.3 (CH3), 27.6 (CH3), 28.0 (CH3), 28.7 (CH3),
70.9 (C-3), 72.5 (C-8), 75.1 (C-7), 81.8 (C-2), 83.3 (C-9), 105.9 (C-
10), 106.0 (C-1), 110.5 (C-4), 115.6 (C-14), 115.8 (C-11) ppm.
HRMS: m/z calcd. for C16H25O8 [M ϩ1]: 345.1549, found
345.1568. C16H24O8 (344.36): calcd. C 55.81, H 7.02; found C
55.90, H 6.84.
Experimental Section
General Remarks: Infrared spectra were recorded on a Bio-Rad
1
FTS-40 spectrometer. H and 13C NMR spectra were acquired on
a Bruker AVANCE DPX-400 spectrometer with chemical shifts (δ)
given in parts per million relative to tetramethylsilane as an internal
standard. Melting points were determined by using open capillaries
and are uncorrected.
Acknowledgments
Compound 3: A solution of 1 (10 g, 34 mmol) and PDC (8 g) in
CH3CN (80 mL) was stirred at 80 °C for 6 h in the presence of
acetic anhydride (9 mL). After evaporation of the solvent under
reduced pressure, the residue was dissolved in EtOAc (300 mL),
filtered through a short silica-gel column, washed with saturated
aqueous NaHCO3 (3 ϫ 50 mL) and the solvents evaporated.
Recrystallization from diethyl ether yielded the product as a white
flake (4.7 g, 81%). M.p. 166Ϫ168 °C. IR (KBr): ν˜ ϭ 1791 cmϪ1
We are grateful to NNSF of P. R. China (No. 20272054) for
financial support of this research. We also thank Dr N. Sugimoto
(Division of Food Additives, NIHS, Kamiyoga 1Ϫ18Ϫ1, Setagaya,
Tokyo 158Ϫ8501, Japan) for the MS measurements.
[1] [1a]
T. Iwasa, T. Kusuka, K. Suetomi, J. Antibiot. 1978, 31,
[1b]
511Ϫ518.
S. Harada, T. Kishi, J. Antibiot. 1978, 31,
519Ϫ524. [1c] S. Harada, E. Mizuta, T. Kishi, Tetrahedron 1981,
37, 1317Ϫ1327.
1
(CϭO). H NMR (400 MHz, CDCl3, 25 °C, TMS): δ ϭ 1.40 (s, 3
H, CH3), 1.44 (s, 3 H, CH3), 1.46 (s, 3 H, CH3), 1.50 (s, 3 H, CH3),
[2] [2a]
A. Takatsuki, K. Arima, G. Tamura, J. Antibiot. 1971, 24,
[2b]
2
3
3
215Ϫ223.
224Ϫ231.
A. Takatsuki, G. Tamura, J. Antibiot. 1971, 24,
A. Takatsuki, G. Tamura, J. Antibiot. 1971, 24,
1.96 (ddd, J
ϭ 14.4, J
ϭ 6.4, J
ϭ 3.2 Hz, 1 H, 5Ј-
H,H
2
H,H
3
H,H
3
[2c]
H), 2.17 (ddd, J
ϭ 14.4, J H,H ϭ 10.8, J
ϭ 7.2 Hz, 1 H,
H,H
H,H
232Ϫ238. [2d] A. Takatsuki, K. Kawamura, M. Okina, Y. Kod-
ama, T. Ito, G. Tamura, Agric. Biol. Chem. 1977, 41,
2307Ϫ2309.
3
5-H), 2.42 (m, 2 H, 6-H and 6Ј-H), 4.78 (d, JH,H ϭ 4.0 Hz, 1 H,
2-H), 5.17 (m, 1 H, 9-H), 5.94 (d, 3JH,H ϭ 5.2 Hz, 1 H, 10-H), 6.14
(d, JH,H ϭ 4.0 Hz, 1 H, 1-H) ppm. 13C NMR (100 MHz, CDCl3,
3
[3] [3a]
D. R. Mootoo, B. Fraser-Reid, J. Org. Chem. 1987, 52,
[3b]
25 °C, TMS): δ ϭ 17.4 (C-6), 25.1 (C-5), 27.2 (CH3), 27.6 (CH3),
27.7 (CH3), 27.9 (CH3), 76.4 (C-2), 80.4 (C-9), 100.2 (C-4), 101.9
(C-1), 103.9 (C-10), 112.9 (C-11), 116.1 (C-14), 129.6 (C-8), 137.6
(C-7), 201.2 (C-3) ppm. HRMS: m/z calcd. for C16H20O8 [M]:
340.1158, found 340.1150. C16H20O8 (340.33): calcd. C 56.47, H
5.92; found C 56.62, H 6.05.
4511Ϫ4517.
D. R. Mootoo, B. Fraser-Reid, J. Org. Chem.
1989, 54, 5548Ϫ5550.
[4]
[5]
M. Jørgensen, E. H. Iversen, R. Madsen, J. Org. Chem. 2001,
66, 4625Ϫ4629.
´
S. Jarosz, S. Skora, K. Szewczyk, Z. Ciunik, Tetrahedron:
Asymmetry 2001, 12, 1895Ϫ1905.
[6]
[7]
S. Jarosz, J. Carbohydr. Chem. 2001, 20, 93Ϫ107.
J. Marco-Cotelles, E. D. Opazo, N. Arroyo, Tetrahedron 2001,
57, 4729Ϫ4739.
Compound 4: A solution of 3 (1 g, 2.9 mmol) and NaBH4 (0.11 g,
2.9 mmol) in ethanol (50 mL) was stirred at room temperature for
1 h. After evaporation of the solvent under reduced pressure, the
residue was dissolved in water (60 mL), extracted with EtOAc (3 ϫ
20 mL), dried (Na2SO4), and the solvents evaporated. After recrys-
tallization from diethyl ether, the product was obtained as a color-
less needle (0.97 g, 96%). M.p. 141Ϫ142 °C. IR (KBr): ν˜ ϭ 3520
[8]
[9]
H.-D. Junker, N. Phung, W.-D. Fessner, Tetrahedron Lett. 1999,
40, 7063Ϫ7066.
S. Jarosz, P. Salanski, M. Mach, Tetrahedron 1998, 54,
2583Ϫ2594.
´
[10]
[11]
Y. Araki, T. Endo, Y. Arai, M. Tanji, Y. Ishido, Tetrahedron
Lett. 1989, 30, 2829Ϫ2832.
K. S. Kim, I. H. Cho, Y. H. Joo, I. Y. Yoo, J. H. Song, J. H.
Ko, Tetrahedron Lett. 1992, 33, 4029Ϫ4032.
1
cmϪ1 (OH). H NMR (400 MHz, [D6]acetone, 25 °C, TMS): δ ϭ
1.38 (s, 6 H, CH3), 1.43 (s, 3 H, CH3), 1.51 (s, 3 H, CH3), 1.89 (m,
Eur. J. Org. Chem. 2004, 2103Ϫ2106
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2105