(m, 1 H), 5.56 (d, J 3, 1 H), 5.59 (d, J 3, 1 H), 5.64 (m, 3 H),
5.72 (d, J 3, 1 H), 8.50 (brs, 1 H); dC(D2O, 353 K, 100 MHz)
22.2, 37.3, 52.2, 60.6, 61.6, 61.7, 62.1, 69.7, 71.2, 71.5, 72.1, 72.7,
72.8, 72.9, 73.1, 73.2, 73.3, 73.8, 74.0, 74.2, 74.4, 74.5, 75.9, 76.4,
78.0, 79.4, 81.9, 82.3, 82.4, 84.0, 88.1, 102.1, 102.4, 102.5, 104.0,
127.2, 145.9, 171.5; MALDI: m/z = 1441 [M+Na]+; HRMS calcd
for C53H87N4O40 [M+H]+: 1419.4897; found: 1419.4887; calcd for
C53H86N4O40Na [M+Na]+: 1441.4716; found: 1441.4726; calcd for
C53H86N4O40K [M+K]+: 1457.4455; found: 1457.4489.
(s, 4 H), 4.20 (d, J 3, 4 H); dC(CDCl3, 298 K, 100 MHz) 58.4, 68.9,
74.6, 79.5.
1,10-Bis(propargyloxy)decane (9)34. NaH (0.86 g, 34 mmol)
was added to a so◦lution of 1,10-decanediol (1 g, 0.06 mol) in
DMF (15 cm3) at 0 C. After 15 min, propargyl bromide (1.5 cm3,
17 mmol) was added. The reaction mixture was stirred overnight
and evaporated under reduced pressure. The residue was diluted
in water (50 cm3) and extracted with ether (2 ¥ 50 cm3). The
dried organic layers (Na2SO4) were then evaporated under reduced
pressure and purified by column chromatography (petroleum
ether/EtOAc 98:2) to give 9 as a liquid (1.12 g, 78%). dH(CDCl3,
298 K, 400 MHz) 1.27 (m, 12 H), 1.57 (m, 4 H), 2.38 (m, 2 H),
3.48 (t, J 7, 4 H), 4.11 (m, 4 H); dC(CDCl3, 298 K, 100 MHz) 26.2,
29.5, 29.7, 58.2, 70.5, 74.1, 80.3; MS-ESI: m/z = 289 [M+K]+, 268
[M+NH4]+, 251 [M+H]+.
1,10-Diazidodecane (5)32. A solution of 1,10-dibromodecane
(5 cm3, 0.02 mol) and sodium azide (5.8 g, 89 mmol) in DMF
(50 cm3) was stirred overnight at 60 ◦C. The mixture was
evaporated under reduced pressure and the residue was diluted
in water (150 cm3) and extracted with CH2Cl2 (2 ¥ 150 cm3). The
combined organic layers were dried with Na2SO4 and evaporated
under reduced pressure. The residue was purified by column
chromatography (petroleum ether/EtOAc 95:5) to give 5 as a
liquid (4.79 g, 96%). dH(CDCl3, 298 K, 400 MHz) 1.30 (m, 12 H),
1.58 (m, 4H), 3.23 (t, J 7, 4 H); dC(CDCl3, 298 K, 100 MHz) 26.8,
29.0, 29.2, 29.5, 51.6.
Bis-lactosyl-didecane (10). Sodium ascorbate (0.014 g,
0.07 mmol) and copper sulfate (0.012 g, 0.07 mmol) were added
to a solution of 8 (0.010 g, 0.07 mmol) and 6 (0.094 g, 0.14 mmol)
in 1:1 H2O/iPrOH (2 cm3). The solution was stirred overnight
and the solvents evaporated under reduced pressure. The residue
was purified by column chromatography (CH3CN/H2O 85:15
to 8:2) over silica gel followed by filtration through reverse
phase C8 cartridge to give 10 as an amorphous white solid after
Lactosyl-decane-azido conjugate (6) and bis-lactosyl-decane (7).
Sodium ascorbate (321 mg, 2 mmol) and copper sulfate (400 mg,
2 mmol) in water (4 cm3 each) were added to a solution of
compound 1 (0.85 g, 2 mmol) and 1,10-diazidodecane 5 (6.8 g,
30 mmol) in DMF (120 cm3). The reaction mixture was stirred
for 3h and concentrated under reduced pressure. The residue was
purified by column chromatography (CH3CN/H2O 95:5 to 75:25)
and freeze-dried, affording 6 (0.75 g, 57%) and 7 (0.6 g, 28%) as
20
lyophilization (0.07 g, 70%). [a]D +14.6 (c = 0.5, H2O); dH(D2O,
353 K, 400 MHz) 1.70 (m, 24 H), 2.36 (brs, 4 H), 2.76 (m,
6 H), 4.17 (dd, J 10 and 8, 2 H), 4.22–4.38 (m, 24 H), 4.49
(m, 2 H), 4.53 (d, J 3, 2 H), 4.87 (m, 8 H), 5.05 (d, J 8, 2 H),
5.16 (m, 8 H), 8.52 (m, 4 H); dC(D2O, 353 K, 100 MHz) 22.3,
26.8, 29.2, 29.5, 30.3, 30.4, 37.3, 51.3, 51.4, 61.6, 62.0, 64.5,
69.7, 70.1, 72.1, 73.9, 75.9, 76.4, 78.0, 79.7, 88.1, 104.1, 125.3,
146.1, 175.5; MS-MALDI: m/z = 1451 [M+Na]+; HRMS calcd
for C62H104N14O24Na [M+Na]+: 1451.7246, found: 1451.7255;
calcd for C62H103N14O24Na2 [M-H+2Na]+: 1473.7065, found:
1473.7079.
20
amorphous white solids. Data for 6: [a]D +12.2 (c = 0.5, H2O);
dH(D2O, 353 K, 400 MHz) 1.89 (m, 12 H), 2.14 (quint, J 7, 2 H),
2.42 (brt, J 7, 2 H), 2.74 (brs, 3 H), 3.81 (t, J 7, 2 H), 4.17 (dd,
J 10 and 8, 1 H), 4.22–4.40 (m, 10 H), 4.48 (d, J 12, 1 H), 4.53 (d,
J 3, 1 H), 4.88 (brt, J 7, 2 H), 5.05 (d, J 8, 1 H), 5.19 (m, 2 H),
8.40 (brs, 1 H); dC(D2O, 353 K, 100 MHz) 22.4, 27.1, 27.4, 29.5,
29.6, 29.7, 29.9, 30.0, 30.6, 37.3, 51.3, 52.3, 61.7, 62.0, 69.7, 71.2,
72.1, 73.9, 75.9, 76.4, 78.0, 79.7, 88.1, 104.1, 124.9, 146.1, 175.1;
MS-MALDI: m/z = 668 [M+Na]+, 646 [M+H]+; HRMS calcd for
C27H47N7O11Na [M+Na]+: 668.32313; found: 668.3227. Data for
Bis-lactosyl-tridecane (11). Sodium ascorbate (0.024 g,
0.12 mmol) and copper sulfate (0.019 g, 0.12 mmol) were added
to a solution of 9 (0.015 g, 0.06 mmol) and 6 (0.077 g, 0.12 mmol)
in 1:1 H2O/iPrOH (3 cm3). The solution was stirred for 2 h and
the solvents evaporated under reduced pressure. The residue was
purified by column chromatography (CH3CN/H2O 9:1 to 85:15)
over silica gel followed by filtration through a reverse phase C8
cartridge (H2O/CH3OH 10:0 to 4:6) to give 11 as an amorphous
20
7: [a]D +8.6 (c = 0.5, H2O); dH(D2O, 353 K, 400 MHz) 1.76 (m,
12 H), 2.41 (brt, J 7, 4 H), 2.79 (brs, 6 H), 4.16 (dd, J 10 and 8, 2 H)
4.22–4.38 (m, 20 H), 4.50 (dd, J 12 and 2, 2 H), 4.53 (d, J 3, 2 H),
4.93 (brt, J 7, 4 H), 5.04 (d, J 8, 2 H), 5.25 (m, 4 H), 8.45 (brs, 2 H);
dC(D2O, 353 K, 100 MHz) 22.3, 26.5, 28.8, 29.2, 30.1, 37.4, 51.4,
61.6, 62.0, 69.7, 71.1, 72.1, 73.9, 76.0, 76.4, 78.0, 79.5, 88.0, 104.0,
125.4, 146.3, 175.9; MS-MALDI: m/z = 1089 [M+Na]+; HRMS
calcd for C44H74N8O22Na [M+Na]+: 1089.4815; found: 1089.4805;
calcd for C44H74N8O22K [M+K]+: 1105.4555; found: 1105.4591.
20
white solid after lyophilization (0.052 g, 56%). [a]D +7 (c = 0.2,
H2O); dH(D2O, 353 K, 400 MHz) 1.75 (m, 36 H), 2.03 (m, 4 H),
2.36 (m, 8 H), 2.74 (m, 6 H), 3.98 (t, J 7, 4 H), 4.18 (dd, J 10 and
8, 2 H), 4.22–4.39 (m, 20 H), 4.48 (d, J 12, 2 H), 4.53 (d, J 3, 2 H),
4.86 (t, J 7, 8 H), 5.05 (d, J 8, 2 H), 5.09 (brs, 4 H), 5.18 (m, 4 H),
8.40 (brs, 4 H); dC(D2O, 353 K, 100 MHz) 22.4, 26.8, 27.0, 29.5,
29.8, 30.1, 30.2, 30.3, 30.5, 30.8, 37.3, 51.1, 51.2, 61.6, 62.0, 64.6,
69.7, 71.1, 72.1, 73.9, 75.9, 76.4, 78.0, 79.7, 88.1, 104.1, 124.4,
124.9, 145.9, 146.0, 175.0; MS-MALDI: m/z = 1563 [M+Na]+;
HRMS calcd for C70H120N14O24Na [M+Na]+: 1563.8497, found:
1563.8502.
1,2-Bis(propargyloxy)ethane (8)33. NaH (2.15 g, 89 mmol) was
added to a s◦olution of ethylene glycol (1.1 g, 18 mmol) in DMF
(20 cm3) at 0 C. After 15 min, propargyl bromide (6 cm3, 0.05 mol)
was added. The reaction mixture was stirred overnight at room
temperature and evaporated under reduced pressure. The residue
was diluted in water (50 cm3) and extracted with ether (2 ¥ 50 cm3).
The organic layer was dried over anhydrous Na2SO4, filtered and
then evaporated under reduced pressure. Column chromatography
(petroleum ether/EtOAc 80:20 to 75/25) afforded 8 as a liquid
(1.76 g, 71%). dH(CDCl3, 298 K, 400 MHz) 2.41 (t, J 3, 2 H), 3.71
Rotaxane 13. A mixture of lactose-decane-azide 6 (0.023 g,
0.036 mmol) and cyclodextrin 4 (0.051 g, 0.036 mmol) in water
(2 cm3) was allowed to stand at room temperature for 15 min before
1 (0.018 g, 0.043 mmol), sodium ascorbate (2.8 mg, 14.4 mmol) and
1686 | Org. Biomol. Chem., 2009, 7, 1680–1688
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