1H NMR (400 MHz, DMSO-d6): d 7.60 (m, 8H, Ar-H), 7.32
(m, 12H, Ar-H), 5.32 (d, J = 3.2 Hz, 1H, H-1), 4.91 (s, OH),
3.95 (d, J = 7.5 Hz, 1H, H6a), 3.77 (m, 3H, H4¢, H3¢, H5¢), 3.65
(d, J = 9.7 Hz, 1H, H6b), 3.52 (m, 3H, H6¢, H3), 3.35 (m, 3H,
H1¢, H5), 3.18 (dd, J = 3.3 Hz, J = 9.5 Hz, 1H, H2), 3.04 (t, J =
9.3 Hz, 1H, H4), 0.92 (s, 9H, CH3), 0.90 (s, 9H, CH3).
13C NMR (100 MHz, DMSO-d6): 135.7, 134.0, 133.7, 130.2,
128.3 (CAr), 105.5 (C-2¢), 92.7 (C-1), 82.8, 77.6, 75.6, 73.7, 73.2,
72.4, 70.1 (C-2,3,3¢,4,4¢,5,5¢), 66.2 (C-1¢), 63.8, 62.5 (C-6,6¢), 27.2
(CH3), 19.5 (CSi(CH3)3).
13C NMR (100 MHz, CDCl3)): 145.1 (Cq-CH3(Ts)), 135.6,
133.1, 132.8, 132.7, 132.6, 129.9, 127.8 (CAr), 102.3 (C-2¢), 91.6
(C-1), 80.4, 78.3, 77.3, 77.0, 76.7, 74.3, 73.6, 72.5, 71.4, 70.9, 69.6
(C-1¢,2,3,3¢,4,4¢,5,5¢), 64.3, 63.3 (C-6,6¢), 26.8 (CH3(TBDPS),
21.6 (CH3(Ts)), 19.2 (SiC(CH3)3).
IR: nmax (KBr): 3474–3310 (O–H), 2928, 2855 (C–H, satd),
1472 (Si–Ar), 1427, 1361 (C–C–C), 1266 (Si–C), 1176 (C–C–O),
1135 (Si–Ar), 1062 (C–O–C), 825 (Ar) cm-1.
General method for peracetylation
IR: nmax (KBr): 3385 (O–H), 2928, 2855 (C–H, satd), 1472
(Si–Ar), 1427, 1390, 1362 (C–C–C), 1266 (Si–C), 1113 (Si–Ar),
1011 (C–O–C), 824 (Ar) cm-1.
This compound was further characterized as hexaacetate:
1¢,2,3,3¢,4,4¢-hexa-O-acetyl-6,6¢-di-O-tert-butyldiphenylsilyl
sucrose 21
Corresponding substrate (2–5, 8, 9, 12) (ª100 mg) was dissolved
in pyridine (1.5 mL) and 0.5 mL of acetic anhydride was
added. The reaction mixture was placed in the microwave
cavity, and subjected to MW irradiation (max 300 W) at
constant temperature (90 ◦C) for 5 min. The method afforded,
after removal of the solvent and purification by flash column
chromatography (eluent hexane/ethyl acetate 3/1, then 1/1),
the corresponding acetylated sucrose derivatives in 96–98%
yield.
1¢-Bromo-1¢-deoxy-6,6¢-di-O-tert-butyldiphenylsilyl sucrose
13. To a solution of 6,6¢-di-O-tert-butyldiphenylsilyl sucrose
(1.00 g, 1.22 mmol) in pyridine (15 mL) was added Ph3P
(0.48 g, 1.83 mmol), followed by CBr4 (0.61 g, 1.83 mmol) in
pyridine (5 mL) dropwise while maintaining the temperature at
1¢,2,3,3¢,4,4¢,6¢-Hepta-O-acetyl- 6-O-methacryloyl sucrose 15.
Faint yellow oil;
0
◦C. Then the reaction mixture was subjected to microwave
[a]2D0 +31.3 (c 1.0, CHCl3); no report.
irradiation of max 300 W at constant temperature 90 ◦C for
10 min. Then the reaction mixture was cooled to rt, quenched
with methanol and the solvents were evaporated under
reduced pressure to give a residue which was purified by flash
column chromatography (eluent, ethyl acetate/acetone/water
100/100/1, then 10/10/1) to afford pure 1¢-bromo-1¢-deoxy-
6,6¢-di-O-tert-butyldiphenylsilyl sucrose 13 (0.35 g, 33%) as
faint yellow oil.
1H NMR (400 MHz, CDCl3): 6.21 (1H, d, JCH2a-CH2b = 13.6 Hz,
CH2a), 5.70 (1H, d, J1-2 = 3.6 Hz, H1), 5.63 (1H, d, JCH2b-CH2a =
C
10.8 Hz, C CH2b), 5.46 (1H, d, J3¢-4¢ = 4.8 Hz, H3¢), 5.44 (1H, t,
J2-3 = J3-4 = 9.9 Hz, H3), 5.38 (1H, t, J3¢-4¢ = J4¢-5¢ = 4.8 Hz, H4¢),
5.13 (1H, t, J3-4 = J4-5 = 9.8 Hz, H4), 4.82 (1H, dd, J1-2 = 3.7 Hz,
J2-3 = 10.4 Hz, H2), 4.28 (8H, m, H5, H6¢, H6, H5¢, H1¢), 2.18 (3H,
s, CH3O), 2.12 (3H, s, CH3O), 2.11 (3H, s, CH3O), 2.10 (3H,
s, CH3O), 2.03 (3H, s, CH3O), 2.02 (3H, s, CH3O), 1.97 (3H, s,
–CH3).
13C NMR (100 MHz, CDCl3): 170.5–169.4 (8-COO–), 135.9
(COO(CH3)C ), 127.6 (CH2 ), 104.1 (C2¢), 90.0 (C1), 79.2
(C5¢), 75.8 (C3¢), 75.1 (C4¢), 70.3 (C2), 69.8 (C3), 68.6 (C5), 68.4
(C4), 63.6 (C6¢), 62.9 (C1¢), 60.7 (C6), 20.6 (7CH3CO), 17.8 (CH3).
IR: nmax (KBr): 2957, 2932, 2857 (C–H, satd), 1756 (C O),
1428, 1370 (C–C–C), 1221 (C–O–C ester), 1178 (C–C–O; C C),
1038 (C–O–C) cm-1.
TOF MS FI: Calcd for C30H40O19: (M)+ 704.22; Found: 704.22
MALDI-TOF MS: Calcd for C30H40O19 ([M+Na]+): 727.21,
found 727.26
[a]2D0 +32.2 (c 1.0, CH3OH); no report.
1H NMR (400 MHz, CDCl3): 7.57 (m, 8H, Ar-H), 7.25 (m,
12H, Ar-H), 5.15 (s, 1H, H-1), 3.96 (m, 3H), 3.79 (m, 1H), 3.73
(m, 1H), 3.68 (m, 4H), 3.44 (m, 4H), 0.93 (s, 9H, CH3), 0.90 (s,
9H, CH3).
13C NMR (100 MHz, CDCl3): 135.6, 133.0, 132.5, 129.8, 127.8
(CAr), 101.8 (C-2¢), 93.3 (C-1), 81.6, 79.2, 74.6, 74.1, 73.6, 72.5,
67.1, 65.6 (C-2,3,3¢,4,4¢,5,5¢), 65.0, 64.7 (C-6,6¢), 34.9 (C-1¢), 26.8
(CH3), 19.2 (SiC(CH3)3).
1¢-O-(p-Toluenesulfonyl)-6,6¢-di-O-tert-butyldiphenylsilyl su-
crose 14. To a solution of 6,6¢-di-O-tert-butyldiphenylsilyl
sucrose (1.00 g, 1.22 mmol) in pyridine (15 mL) was added
p-toluenesulfonyl chloride (0.35 g, 1.83 mmol). This mixture
was subjected to microwave ◦irradiation of max 300 W for 5 min
at constant temperature 90 C. Then the reaction mixture was
concentrated and the residue was purified by flash column chro-
matography (eluent, ethyl acetate/acetone/water 100/100/1,
then 10/10/1) to afford pure 1¢-O-(p-toluenesulfonyl)-6,6¢-di-
O-tert-butyldiphenylsilyl sucrose 14 (0.31 g, 26%) as colourless
solid.
1¢,2,3,3¢,4,4¢,6¢-Hepta-O-acetyl-6-O-crotonoyl sucrose 16.
Faint yellow oil;
[a]2D0 +43.2 (c 1.1, CHCl3); no report.
1H NMR (400 MHz, CDCl3): 7.01 (1H, m, CH CH–CH3),
6.85 (1H, m, CH CH–COO), 5.69 (1H, d, J1-2 = 3.5 Hz, H1),
5.46 (2H, m, H3, H3¢), 5.37 (1H, t, J3¢-4¢ = J4¢-5¢ = 5.8 Hz, H4¢), 5.08
(1H, t, J3-4 = J4-5 = 9.7 Hz, H4), 4.88 (1H, dd, J1-2 = 3.6 Hz, J2-3
=
10.3 Hz, H2), 4.29 (5H, m, H5, H6¢a,b, H6a,b), 4.17 (2H, s, H1¢a,b),
4.16 (1H, m, H5¢), 2.18 (3H, s, CH3O), 2.12 (6H, s, 2CH3O), 2.11
(3H, s, CH3O), 2.10 (3H, s, CH3O), 2.05 (3H, s, CH3O), 2.02
(3H, s, CH3O), 1.90 (3H, t, JCH2-CH3 = 7.0 Hz, CH3).
13C NMR (100 MHz, CDCl3): 170.5–169.5 (8-COO-), 148.9
(CH3CH CH), 121.3 (–COO–CH CH), 104.1 (C2¢), 89.9 (C1),
79.1 (C5¢), 75.7 (C3¢), 75.0 (C4¢), 70.3 (C2), 69.6 (C3), 68.4 (C5),
68.1 (C4), 63.6 (C6¢), 62.8 (C1¢), 61.9 (C6), 20.6 (7CH3CO), 17.9
(CH3).
[a]2D0 +29.5 (c 1.1, CH3OH); no report.
m.p. 152–154 ◦C; lit. no report.
1H NMR (400 MHz, CDCl3): 7.76 (d, J = 7.5 Hz, 2H, Ar-
H(Ts)), 7.65 (m, 6H, Ar-H), 7.57 (d, J = 6.5 Hz, 1H, Ar-H(Ts)),
7.30 (m, 14H, Ar-H), 5.49 (s, 1H, H-1), 4.19 (m, 1H), 4.14 (s,
2H), 4.00 (s, 1H), 3.90 (s, 1H), 3.75 (m, 6H), 3.62 (m, 2H), 3.46
(s, 1H), 3.40 (t, J = 8.6 Hz, 1H), 2.39 (s, 3H, CH3(Ts)), 1.03 (s,
9H, CH3), 1.02(s, 9H, CH3).
1904 | Green Chem., 2011, 13, 1897–1906
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The Royal Society of Chemistry 2011
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