Gal-glycopolymer 6
J = 4.0 Hz, 1 H); 13C NMR (Cl3CD, 75 MHz): d = 170.9–
169.30 (19 peaks), 143.7, 125.9, 100.3, 97.15, 97.1, 96.8, 96.8, 96.7,
96.6, 96.5, 77.5, 77.3, 77.1, 76.9, 76.7, 76.5, 75.9, 71.5, 71.3, 71.1,
70.9, 70.8, 70.5, 70.5, 70.3, 70.2, 70.0, 69.8, 69.7, 69.5, 69.4, 68.8,
67.2, 62.8, 62.7, 62.5, 62.3, 61.3, 49.4, 20.8, 20.8, 20.7, 20.6; MS
(MALDITOF): m/z: calcd for C99H131N3 O64Na: 2408.7 [M +
Na]+; found 2408.8.
Obtained in 79% yield: IR (KBr): m = 3484, 1663, 1498, 1390,
1256, 1100 cm−1; 13C NMR (DMSO-d6, 75 MHz): d = 144.5,
133.6, 128.0, 125.0, 103.2, 75.6, 73.8, 71.0, 68.6, 61.9, 61.0, 53.0.
Lac-glycopolymer 7
Obtained in 82% yield: IR (KBr): m = 3430, 1663, 1498, 1439,
1389, 1256, 1097 cm−1; 13C NMR (DMSO-d6, 75 MHz): d = 144.0,
127.8, 124.7, 103.9, 101.9, 80.8, 75.5, 74.9, 73.3, 70.6, 68.2, 61.7,
60.5, 53.0.
Monovalent Lac(OAc)-glycocyclodextrin 15
Column chromatography (AcOEt) gave 15 (75%) as a solid: mp
156–158 ◦C; [a]D = +80 (c = 1 in chloroform); IR (KBr): m = 1750,
1
1371, 1232, 1046 cm−1; H NMR (Cl3CD, 300 MHz) (selected
General procedure for the synthesis of fluorescent glycopolymers 8
and 9
signals): d = 7.63 (s, H-triazole); 13C NMR (Cl3CD, 75 MHz): d =
170.9–169.0 (17 peaks), 143.8, 126.0, 101.0, 100.8, 99.7, 97.1, 97.0,
96.8, 96.6, 96.5, 83.2, 80.9, 77.2, 77.0, 76.2, 76.0, 75.8, 75.1, 74.7,
74.4, 74.3, 74.1, 72.7, 71.6, 71.5, 71.3, 71.0, 70.7, 70.5, 70.4, 70.2,
70.1, 70.0, 69.7, 69.4, 69.1, 68.4, 66.7, 62.6, 62.3, 62.1, 60.8, 60.2,
60.0, 59.3, 58.7, 55.9, 49.4, 20.8, 20.6, 20.5; MS (MALDITOF):
m/z: calcd for C119H189N21O77Na: 3167.1 [M + Na]+; found: 3167.1.
A solution of the polystyrene derivative 3 (0.100 g), the propargyl
dansyl derivative 530 (0.03 mmol, 0.05 equiv. per azide group)
and the copper catalyst [(EtO)3P·CuI] (0.063 mmol, 0.1 equiv. per
alkyne group) in DMF (10 mL) was irradiated at 800 W and
90 ◦C in a Milestone Star Microwave Labstation until the IR
spectra of the reaction mixture showed complete disappearance of
the starting material (15 min). At this moment, the correspond-
ing propargyl sugar derivative 4a,b (0.76 mmol, 1.2 equiv. per
alkyne group) was added and the reaction mixture irradiated for
additional 15 min. The work-up procedure was identical as that
indicated for the synthesis of non-fluorescent glycopolymers 6, 7.
Heptavalent Gal(OAc)-glycocyclodextrin 18
Column chromatography (CH2Cl2–MeOH 20 : 1) gave 18 (88%)
as a solid: mp 184–186 ◦C; [a]D = +7.5 (c = 1 in chloroform);
[a]436
=
10.0 (c 1, chloroform); IR (KBr):
m
=
1752,
1372, 1228, 1048 cm−1; 1H NMR (Cl3CD, 300 MHz) (se-
lected signals): d = 7.76 (s; H-triazole); 13C NMR (DMSO-
d6, 75 MHz): d = 170.4, 170.3, 169.5, 144.2, 125.8, 100.8,
96.4, 84.5, 70.8, 69.8, 68.7, 67.1, 65.5, 61.1, 20.8, 20.6;
MS (MALDITOF): m/z: calcd for C184H245N21O112Na: 4623.8
[M + Na]+; found: 4624.0.
Fluorescent Gal-glycopolymer 8
Obtained 0.179 g. IR (KBr): m = 3386, 1644, 1513, 1226, 1141,
1067 cm−1; 1H NMR (DMSO-d6, 300 MHz) (selected signals): d =
8.12 (br s; H-triazole), 6.90. 6.35 (2 br s; Ar); 13C NMR (DMSO-
d6, 75 MHz): d = 144.7, 144.0, 127.5, 127.3, 127.1, 124.4, 124.2,
102.6, 75.1, 73.2, 70.4, 68.0, 61.3, 60.3, 52.5.
Heptavalent Lac(OAc)-glycocyclodextrin 19
Fluorescent Lac-glycopolymer
Column chromatography (AcOEt then AcOEt–MeOH 30 : 1)
gave 19 (87%) as a solid: mp 194–196 ◦C; [a]D = +14.5 (c = 1
Obtained 0.313 g. IR (KBr): m = 3384, 2921, 1644, 1054 cm−1;
1H NMR (DMSO-d6, 300 MHz) (selected signals): d = 8.15 (br s;
H-triazole), 6.91, 6.33 (2 br s; Ar), 5.47 (br s; ArCH2N); 13C NMR
(DMSO-d6, 75 MHz): d = 143.8, 132.8, 127.3, 124.5, 103.98, 101.8,
80.7, 75.4, 74.9, 73.2, 70.5, 68.1, 61.6, 60.4, 52.4.
1
in chloroform); IR (KBr): m = 1750, 1370, 1225, 1047 cm−1; H
NMR (Cl3CD, 300 MHz) (selected signals): d = 7.76 (br s, 7
H; H-triazole), 5.36 (br s, 7 H; H-4ꢀ lactose), 5.25–3.50 (several
m), 2.15, 2.05, 2.03, 1.97, 1.93 (5 s, 189 H; 63 × Ac); 13C NMR
(Cl3CD, 75 MHz): d = 170.4, 170.2, 170.1, 169.8, 169.6, 169.2,
144.0, 126.0, 100.9, 100.2, 96.4, 76.1, 72.7, 71.5, 71.0, 70.5, 69.7,
69.0, 66.6, 63.0, 62.0, 60.7, 60.4, 50.1, 21.2, 20.9, 20.8, 20.7, 20.5;
MS (MALDITOF): m/z: calcd for C184H245N21O112Na: 4623.8
[M + Na]+; found: 4624.0.
General procedure for the synthesis of non-fluorescent
glycocyclodextrins functionalized at the primary face 14, 15, 18
and 19
A solution of the 6-azido cyclodextrin derivative 1024 or 1125
(0.100 mmol), the corresponding propargyl sugar derivative 4a,b
(1.3 equiv. per azide group) and the copper catalyst [(EtO)3P·CuI]
(0.1 equiv. per azide group) in toluene (15 mL) was refluxed
for 1.5 h. The reaction mixture was evaporated and the crude
purified by column chromatography to yield the corresponding
glycocyclodextrin.
Synthesis of fluorescent glycocyclodextrin functionalized at the
primary face (22)
A solution of the 6-azido cyclodextrin derivative 11 (0.100 g),
the propargyl dansyl derivative 5 (0.15 mmol, 0.25 equiv. per
azide group) and the copper catalyst [(EtO)3P·CuI] (0.063 mmol,
0.1 equiv. per azide group) in DMF (5 mL) was irradiated at
800 W and 90 ◦C in a Milestone Star Microwave Labstation
for 6 h. At this moment, the corresponding propargyl sugar
derivative 4a (0.76 mmol, 1.2 equiv. per alkyne group) was
added and the reaction mixture irradiated for an additional 2 h.
The work-up procedure was identical to that indicated for the
synthesis of non fluorescent glycocyclodextrins 14, 15, 18 and
Monovalent Gal(OAc)-glycocyclodextrin 14
Column chromatography (AcOEt–hexane 10 : 1 to AcOEt) gave
14 (79%) as an amorphous solid: [a]D = +97 (c = 1 in chloroform);
1
IR (KBr): m = 1750, 1372, 1235, 1047 cm−1; H NMR (Cl3CD,
300 MHz) (selected signals): d = 7.63 (s; H-triazole), 5.60 (d,
2298 | Org. Biomol. Chem., 2007, 5, 2291–2301
This journal is
The Royal Society of Chemistry 2007
©