38
H.-M. Chen et al./Carbohydrate Research 421 (2016) 33–39
(3.0 g, 1.4 equiv) were added dropwise a solution of DIAD (2.19 g,
4.3.13. 6-Chloro-4-methylumbelliferyl β-lactoside
1
.4 equiv) in dry toluene (15 mL) with stirring under N at room tem-
2
See general procedure 4.2.3. The product was obtained as a white
1
perature. After addition, the reaction mixture was stirred for 1.5 h
at the same condition. The reaction mixture was diluted with EtOAc
solid in 95% yield. H NMR (d
6 2
-DMSO + D O, 400 MHz): δ 7.84 (s, 1
H, Ar-H), 7.30 (s, 1 H, Ar-H), 6.30 (d, 1 H, J 1.2 Hz, Ar-H), 5.26 (d, 1
H, J1,2 7.6 Hz, H-1), 4.24 (d, 1 H, J1′,2′ 7.2 Hz, H-1′), 3.77~3.32 (m, 12
(
(
200 mL), washed with 1 M NaOH (100 mL), saturated NaHCO
2 × 100 mL) and brine (100 mL), dried over MgSO , filtered and con-
3
13
4
H, remaining protons of sugar ring), 2.50 (s, 3 H, Ar-CH
3
). C NMR
centrated. The resulting residue was purified by flash column
chromatography (5:1, petroleum ether-ethyl acetate with 1% tri-
ethylamine) to give the product containing some impurities. The
(d -DMSO + D O, 100 MHz): δ 160.4, 155.4, 153.5, 153.4, 126.6, 118.7,
6
2
115.3, 113.3, 104.4, 100.0, 96.0, 80.4, 76.1, 75.7, 75.4, 73.6, 73.2, 71.0,
+
68.6, 61.0, 60.4, 18.7. ESI-HRMS: Calcd for [C22
557.1038. Found m/z: 557.1025.
H
27ClO13 + Na] :
2
crude product was reacted with AcOH/H O (40 mL/10 mL) for 2 h
at 100 °C; then, the solvent was evaporated under reduced pres-
sure to give a white solid, which was filtered and washed with
methanol. The white solid was suspended in methanol, heated to
reflux for 1 h with stirring, then cooled to room temperature. The
4.3.14. 6-Chloro-4-methylumbelliferyl
2,2′,3,3′,4′,6,6′-hepta-O-acetyl-β-cellobioside
21
See general procedure 4.2.1. and 4.2.2., eluent (1:1, petroleum
precipitate was filtered and washed with methanol to afford the
ether-ethyl acetate); the product was obtained as a white solid in
1
1
desired product (1.55 g) in 52% overall yield. H NMR (d
6
2
-DMSO + D O,
53% yield. H NMR (d
6
-DMSO, 400 MHz): δ 7.88 (s, 1 H, Ar-H), 7.23
4
00 MHz): δ 7.85 (s, 1 H, Ar-H), 7.24 (s, 1 H, Ar-H), 6.32 (s, 1 H, Ar-
(s, 1 H, Ar-H), 6.35 (s, 1 H, Ar-H), 5.62 (d, 1 H, J1,2 8.0 Hz, H-1), 5.29
(t, 1 H, J2,3 = J3,4 9.6 Hz, H-3), 5.28 (t, 1 H, H-3′), 5.09 (dd, 1 H, J2,3 9.6 Hz,
H-2), 4.90 (t, 1 H, J3′,4′ = J4′,5′ 9.6 Hz, H-4′), 4.87 (d, 1 H, J1′,2′ 8.0 Hz,
H-1′), 4.67 (dd, 1 H, J2′,3′ 9.6 Hz, H-2′), 4.44 (brd, 1 H, H-6a), 4.25 (m,
2 H, H-5 & H-6a′), 4.13 (dd, 1 H, J5,6b 7.6 Hz, J6a,6b 12.0 Hz, H-6b), 4.02
(m, 1 H, H-5′), 3.97 (dd, 1 H, J5,6b′ 2.0 Hz, J6a′,6b′ 12.4 Hz, H-6b′), 3.92
H), 5.37 (brs, 1 H, H-1), 3.93 (brs, 1 H, H-2), 3.75~3.39 (m, 5 H,
remaining protons of sugar ring), 2.42 (s, 3 H, Ar-CH
DMSO + D O, 100 MHz): δ 160.3, 155.5, 153.5, 153.3, 126.5, 118.7,
1
13
3 6
). C NMR (d -
2
15.2, 113.2, 104.7, 98.7, 78.6, 73.8, 70.7, 67.3, 61.6, 18.7. ESI-
+
HRMS: Calcd for [C16
H17ClO
8
+ Na] : 395.0510. Found m/z: 395.0515.
(
t, 1 H, J4,5 9.6 Hz, H-4), 2.40 (d, 3 H, J 0.8 Hz, Ar-CH
3
), 2.12 (s, 3 H,
CH
CH
3
CO), 2.03 (s, 6 H, 2 × CH
3
CO), 2.01 (s, 3 H, CH
6
CO). C NMR (d -
3
CO), 1.99 (s, 3 H,
4
.3.10. 6-Chloro-4-methylumbelliferyl
1
3
3
CO), 1.98 (s, 3 H, CH CO), 1.93 (s, 3 H, CH
3
3
2,3,4-tri-O-acetyl-α-L-fucopyranoside
DMSO, 100 MHz): δ 170.8, 170.6, 170.2, 170.0, 169.8, 169.63, 169.57,
60.0, 154.5, 153.3, 153.1, 127.2, 118.7, 116.3, 113.9, 105.0, 100.1,
98.1, 76.9, 72.9, 72.6, 72.3, 71.8, 71.1, 70.9, 68.3, 62.6, 62.2, 21.11, 21.05,
See general procedure 4.2.1. and 4.2.2., eluent (2:1, petroleum
1
ether-ethyl acetate); the product was obtained as a white solid in
8
1
1
1% yield. H NMR (CDCl
3
, 400 MHz): δ 7.63 (s, 1 H, Ar-H), 7.21 (s,
2
1.0 (2 C), 20.9, 20.8, 20.7, 18.7. ESI-HRMS: Calcd for
H, Ar-H), 6.28 (s, 1 H, Ar-H), 5.63 (dd, 1 H, J2,3 10.6 Hz, H-2), 5.38
+
[
C
36
H
41ClO20 + Na] : 851.1777. Found m/z: 851.1790.
(
d, 1 H, H-4), 5.19 (dd, 1 H, J3,4 3.6 Hz, H-3), 5.09 (d, 1 H, J1,2 8.0 Hz,
H-1), 4.07 (q, 1 H, J5,6 6.0 Hz H-5), 2.44 (s, 3 H, Ar-CH ), 2.26 (s, 3
H, CH CO), 2.12 (s, 3 H, CH CO), 2.06 (s, 3 H, CH CO), 1.37 (d, 3 H,
, 100 MHz): δ 170.7, 170.3, 169.4, 160.5, 155.1,
53.2, 151.5, 125.7, 120.2, 116.1, 114.1, 105.4, 100.3, 71.0, 70.3, 69.9,
3
4
.3.15. 6-Chloro-4-methylumbelliferyl β-cellobioside21
3
3
3
13
See general procedure 4.2.3. The product was obtained as a white
H-6). C NMR (CDCl
3
1
solid in 96% yield. H NMR (d
H, Ar-H), 7.29 (s, 1 H, Ar-H), 6.29 (s, 1 H, Ar-H), 5.24 (d, 1 H, J1,2 7.6 Hz,
H-1), 4.30 (d, 1 H, J1′,2′ 8.0 Hz, H-1′), 3.76~2.99 (m, 12 H, remaining
6 2
-DMSO + D O, 400 MHz): δ 7.83 (s, 1
1
6
8.1, 20.9, 20.79, 20.75, 18.8, 16.2. ESI-HRMS: Calcd for
+
[
C
22
H
23ClO10 + Na] : 505.0877. Found m/z: 505.0868.
13
protons of sugar ring), 2.39 (s, 3 H, Ar-CH
3
). C NMR (d
6 2
-DMSO + D O,
1
1
6
00 MHz): δ 160.5, 155.3, 153.4 (2 C), 126.6, 118.7, 115.3, 113.2,
4
.3.11. 6-Chloro-4-methylumbelliferyl α-L-fucopyranoside
04.3, 103.6, 100.0, 80.1, 77.3, 76.8, 75.7, 75.4, 73.8, 73.2, 70.5, 61.5,
See general procedure 4.2.3. The product was obtained as a white
+
0.3, 18.7. ESI-HRMS: Calcd for [C22
H
27ClO13 + Na] : 557.1038. Found
1
solid in 93% yield. H NMR (d
H, Ar-H), 7.23 (s, 1 H, Ar-H), 6.27 (s, 1 H, Ar-H), 5.10 (d, 1 H, J1,2 7.8 Hz,
H-1), 3.88 (q, 1 H, H-5), 3.66~3.40 (m, 3 H, H-2,H-3 & H-4), 2.37 (s,
3
1
1
6 2
-DMSO + D O, 400 MHz): δ 7.81 (s, 1
m/z: 557.1046.
4.3.16. 6-Chloro-4-methylumbelliferyl
3 6 2
H, Ar-CH -DMSO + D O,
), 1.12 (d, 3 H, J5,6 6.6 Hz, H-6). 13C NMR (d
00 MHz): δ 160.3, 155.6, 153.5, 153.3, 126.7, 118.6, 115.0, 113.2,
2,2′,3,3′,4′-penta-O-acetyl-β-xylobioside
Hexa-O-acetyl-xylobiose (1.51 g, 2.8 mmol) was treated with an-
04.0, 100.8, 74.1, 71.4, 71.2, 70.2, 18.7, 17.1. ESI-HRMS: Calcd for
hydrous DCM (20 mL), acetic anhydride (1 mL) and HBr/AcOH
+
[
C
16
H
17ClO
7
+ Na] : 379.0561. Found m/z: 379.0561.
14
(2.6 mL, 30% w/w) for 2.5 h at 0 °C. The reaction mixture was diluted
with DCM (80 mL), washed with cold water (2 × 50 mL), cold NaHCO
(2 × 50 mL) and cold brine (50 mL), dried over MgSO , filtered and
3
4.3.12. 6-Chloro-4-methylumbelliferyl
4
2
,2′,3,3′,4′,6,6′-hepta-O-acetyl-β-lactoside
See general procedure 4.2.1. and 4.2.2., eluent (1:1, petroleum
concentrated to afford a residue α-xylobiosyl bromide as a white
foam. To the foam were added TBAB (2.8 mmol, 1 equiv), DCM
(12 mL) and a solution of 6-chloro-4-methylumbelliferone (1.8 g,
8.5 mmol, 3 equiv) in 5% NaOH (6 mL), and the reaction mixture was
stirred vigorously overnight at room temperature, diluted with DCM
(150 mL), washed with 1 M NaOH (2 × 50 mL), water (50 mL) and
ether-ethyl acetate); the product was obtained as a white solid in
5
1
3% yield. H NMR (d
6
-DMSO, 400 MHz): δ 7.87 (s, 1 H, Ar-H), 7.24
22
(
s, 1 H, Ar-H), 6.35 (s, 1 H, Ar-H), 5.64 (d, 1 H, J1,2 8.0 Hz, H-1), 5.29
dd, 1 H, J3,4 9.2 Hz, H-3), 5.25 (brd, 1 H, H-4′), 5.19 (dd, 1 H, J3′,4′ 3.6 Hz,
H-4′), 5.10 (dd, 1 H, J2,3 9.6 Hz, H-2), 4.88 (dd, 1 H, J2′,3′ 10.0 Hz, H-2′),
.81 (d, 1 H, J1′,2′ 8.0 Hz, H-1′), 4.43 (brd, 1 H, H-6a′), 4.24 (m, 2 H,
H-5 & H-5′), 4.14 (dd, 1 H, J5,6b′ 7.2 Hz, J6a′,6b′ 11.6 Hz, H-6b′), 4.03 (m,
H, H-6a & H-6b), 3.96 (dd, 1 H, J4,5 9.6 Hz, H-4), 2.40 (d, 3 H, J 0.8 Hz,
Ar-CH ), 2.12 (s, 3 H, CH CO), 2.11 (s, 3 H, CH CO), 2.05 (s, 3 H, CH CO),
.03 (s, 3 H, CH CO), 2.02 (s, 6 H, 2 × CH CO), 1.91 (s, 3 H, CH CO).
-DMSO, 100 MHz): δ 170.8, 170.5 (2 C), 170.1, 169.9,
(
4
brine (50 mL), dried over MgSO , filtered and concentrated to give
a slightly yellow solid. The crude product was purified by flash
4
column chromatography (25:1 DCM-acetone) to give the product
1
2
as a white solid (1.19 g, 61%). H NMR (d
6
-acetone, 400 MHz): δ 7.80
3
3
3
3
(s, 1 H, Ar-H), 7.22 (s, 1 H, Ar-H), 6.26 (s, 1 H, Ar-H), 5.51 (d, 1 H,
J1,2 7.2 Hz, H-1), 5.24 (dd, 1 H, J3,4 8.4 Hz, H-3), 5.17 (t, J3′,4′ 8.6 Hz,
H-3′), 5.16 (dd, 1 H, J2,3 8.8 Hz, H-2), 4.90 (dt, 1 H, H-4′), 4.85 (d, 1
H, J1′,2′ 7.2 Hz, H-1′), 4.81 (dd, 1 H, J2′,3′ 8.4 Hz, H-2′), 4.23 (dd, 1 H,
2
3
3
3
1
3
C NMR (d
6
1
1
6
69.7, 169.6, 160.0, 154.5, 153.3, 153.1, 126.9, 118.7, 116.3, 113.8,
05.0, 100.6, 98.0, 76.7, 72.9, 72.6, 71.0, 70.9, 70.4, 69.5, 67.7, 62.6,
J
4,5a 5.2 Hz, J5a,5b 11.6 Hz, H-5a), 4.11 (dd, 1 H, J4,5a′ 4.8 Hz, J5a′,5b′ 12.0 Hz,
H-5a′), 4.07 (dt, 1 H, H-4), 3.82 (dd, 1 H, J4,5b 8.8 Hz, H-5b), 3.55 (dd,
1 H, J4,5b′ 9.0 Hz, H-5b′), 2.47 (s, 3 H, Ar-CH ), 2.09 (s, 3 H, CH CO),
1.5, 21.1 (2 C), 21.0, 20.97, 20.9 (2 C), 20.8, 18.7. ESI-HRMS: Calcd
+
for [C36
H
41ClO20 + Na] : 851.1777. Found m/z: 851.1786.
3
3