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OTBDPS
O
OTBDPS
O
OTBDPS
O
H
OMp
(PO)3
(PO)3
(PO)3
O
N
C
A
B CH3CN
C
OTBDPS
CH3
O
N C CH3
O
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(PO)3
(PO)3
D
E
Scheme 3. The proposed mechanism of the formation of 1,6-anhydro sugar.
Table 2
Synthesis of 1,6-anhydro sugars using HClO4ÁSiO2
13
Entry Substrate
Producta
Time
(min)
Yieldb
(%)
Ref.
9
OH
O
OBn
OBn
O
O
BnO
BnO
k
l
5
85
80
79
BnO
11
OBn
3a
OMp
OH
O
OBz
O
OMp
BzO
O
BzO
10
2
8
9
OBz
OBz OBz
12
6a
OTr
O
OBn
OBn
O
O
BnO
BnO
m
12. Åberg, P.-M.; Ernst, B. Acta Chem. Scand. 1994, 48, 228–233.
BnO
13
OBn
3a
OMp
13. General procedure for the synthesis of 1,6-anhydro sugars: The solution of
glycoside substrate (0.1 mmol) in anhydrous acetonitrile (10 mL) was heated
up to 70 °C under the protection of argon gas, then 20 mol % HClO4ÁSiO2 was
added. The resulting mixture was kept on heating until TLC indicated
completion of the reaction. Acetonitrile was evaporated in vacuo and the
crude residue was purified by column chromatography.
a
Analytical data for all products were consistent with known products from the
literature.
b
Isolated yield.
14. Compound characterization data for compound 1a: (a) Gening, M. L.; Tsvetkov,
Y. E.; Pier, G. B.; Nifantiev, N. E. Russ. J. Bioorg. Chem. 2006, 32, 389–399;
Compound characterization data for compound 2a: (b) Yang, F.; Hua, Y.-X.; Du,
Y.-G. Carbohydr. Res. 2003, 338, 1313–1318; Compound characterization data
for compound 4a: (c) Kayastha, A. K.; Hotha, S. Tetrahedron Lett. 2010, 51,
5269–5272; Compound characterization data for compound 5a: (d) Milos, B.;
Jana, P.; Michaela, H.; Ivana, C.; Tomas, T.; Miloslav, C. Chem. Commun. 2006, 71,
311–336; (e) Compound characterization data for compound 7a: 1H NMR:
(400 MHz, CDCl3): d 8.14 (d, J = 7.1 Hz, 2H), 8.06 (d, J = 7.1 Hz, 2H), 7.63–7.58
(m, 2H), 7.50–7.44 (m, 4H), 5.67 (s, 1H, H-1), 5.30 (s, 1H), 5.01 (s, 1H), 4.81 (s,
1H), 4.70 (d, 1H, J = 5.1 Hz), 4.29 (d, 1H, J = 7.8 Hz), 3.91 (dd, 1H, J = 5.5, 7.4 Hz),
1.58 (s, 9H); 13C NMR (100 MHz, CDCl3): d 117.5, 165.2, 164.7, 133.6, 133.5,
129.9, 129.8, 129.2, 129.1, 128.6, 128.4, 116.0, 114.8, 99.6, 73.8, 70.0, 69.9,
69.4, 65.6, 38.9, 27.0.; (f) Compound characterization data for compound 8a: 1H
NMR: (400 MHz, CDCl3): d 8.12–8.06 (m, 4H), 7.66–7.60 (m, 2H), 7.52–7.56 (m,
4H), 5.71 (s, 1H, H-1), 5.27 (s, 1H), 5.05 (s, 1H), 4.90 (d, 1H, J = 5.2 Hz), 4.63 (s,
1H), 4.19 (d, 1H, J = 7.9 Hz), 3.93 (dd, 1H, J = 6.0, 7.9 Hz), 3.23 (s, 3H); 13C NMR
(100 MHz, CDCl3): d 165.2, 165.0, 134.1, 133.7, 130.0, 129.9, 128.9, 128.8,
128.6, 128.5, 99.3, 70.1, 68.7, 65.2, 38.7.
Acknowledgments
This work is supported by the National Nature Science Founda-
tion of China (NSFC21002014) and the Fundamental Research
Funds for the Central Universities of China.
Supplementary data
Supplementary data associated with this Letter can be found, in
References and notes
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