Y. Nonaka et al. / Tetrahedron 72 (2016) 5456e5464
5463
76.198, 72.868, 72.548, 71.479, 70.953, 70.764, 69.111, 66.612,
62.017, 60.817, 20.831, 20.724, 20.659, 20.527; MALDI-TOF-MS,
[MþNa]þ¼1685.37 (calcd 1685.49); nmax (KBr) 1749, 1509, 1228,
than 10, the resultant mixture was concentrated and kept at the
ambient temperature for 3 days to form white precipitate. The
precipitate was retrieved through filtration and dried over the filter
paper overnight to give the title compound as a white powder
(0.14 g, >99%); dH (300 MHz, DMSO-d6þD2O): 9.24 (s, 2H), 8.60 (d, J
8.1 Hz, 2H), 8.49 (dd, J 1.8, 8.1 Hz, 2H), 7.70 (d, J 8.7 Hz, 4H), 7.09 (d, J
9.0 Hz, 4H), 5.09 (d, J 3.6 Hz, 2H), 4.93 (d, J 7.8 Hz, 2H), 3.77e3.45 (m,
16H), 3.41 (t, J 8.7 Hz, 2H), 3.32 (t, J 8.4 Hz, 2H), 3.27 (dd, J 3.0, 9.6 Hz,
2H), 3.09 (t, J 9.0 Hz, 2H); dC (75 MHz, DMSO-d6þD2O): 163.172,
156.365, 153.792, 148.556, 136.504, 132.829, 130.824, 121.707,
120.449, 116.520, 100.637, 100.497, 78.959, 76.049, 75.252, 73.271,
73.090, 72.712, 72.243, 69.884, 60.767, 60.216; HR-ESI-TOF-MS,
[MþH]þ¼1075.3550 (calcd 1075.3519); 3299, 1653, 1604, 1542,
1054 cmꢁ1
.
4.5. 5,50-Bis-(-N-(p-O-(
2,20-bipyridine (bpyLac)
b-lactosyl)phenyl)-aminocarbonyl)-
To bpyLacAc (0.67 g, 0.40 mmol) in methanol/THF (1:1, 50 ml),
aqueous ammonia was added dropwise until pH value of the re-
sultant mixture became larger than 10. The resultant reaction
mixture was stirred at ambient temperature for overnight. After
confirming that the pH value of the reaction mixture was still larger
than 10, the resultant mixture was concentrated to form white
precipitate. The precipitate was retrieved through filtration and
dried over the filter paper overnight to give the title compound as
a white powder (0.37 g, >99%); dH (300 MHz, DMSO-d6þD2O): 9.04
(s,1H), 8.62 (d, J 4.5 Hz,1H), 8.38e8.29 (m, 3H), 7.92 (td, J 1.2, 7.8 Hz,
1H), 7.55 (d, J 9.0 Hz, 2H), 7.44 (dd, J 5.1, 7.2 Hz, 1H), 7.00 (d, J 9.0 Hz,
2H), 4.86 (d, J 7.5 Hz, 1H), 4.19 (t, J 3.6 Hz, 1H), 3.61 (d, J 10.8 Hz, 1H),
3.62e3.56 (m, 2H), 3.50e3.38 (m, 6H), 3.30e3.25 (m, 3H); dC
(75 MHz, DMSO-d6þD2O): 164.612, 157.163, 154.614, 149.394,
137.729, 133.290, 131.646, 122.998, 121.781, 117.292, 104.197,
100.810, 80.234, 76.131, 75.507, 75.235, 73.591, 73.468, 71.248,
68.881, 61.260, 60.586; HR-ESI-TOF-MS, [MþH]þ¼1075.3550 (calcd
1075.3519); nmax (KBr) 3375, 1647, 1542, 1508, 1417, 1224,
1509, 1434, 1225, 1040 cmꢁ1
.
4.8. 5,50-Bis-(-N-(p-O-(2,3,6,20,30,40,60-hepta-O-acetyl-
b-cello-
biosyl)phenyl)-aminocarbonyl)-2,20-bipyridine (bpyCelAc)
To pAPCel (0.49 g, 0.67 mmol) and Et3N (2.0 ml) in THF (50 ml),
a THF solution (5.0 ml) containing bpyCOCl prepared from 0.08 g
(0.33 mmol) of bpyCOOH was added and then, the resultant mix-
ture was stirred at the ambient temperature for 20 min. The re-
sultant reaction mixture was poured into iced water and diluted
with ethyl acetate. The organic layer was washed with 0.5 N HCl aq
and NaHCO3 saturated aqueous solution repeatedly. The organic
layer was dried over anhydrous MgSO4 for overnight. After this
overnight drying process, we found that large amount of white
precipitate was formed in the flask. To separate the precipitate and
the MgSO4 powder, the resultant mixture was filtered, and the
white solid (a mixture of bpyCelAc and the MgSO4) on the filter
paper was washed with water repeatedly to remove MgSO4. The
resultant white solid (bpyCelAc) was dissolved into CHCl3/MeOH
(100:1) to be corrected in a round bottom flask. The resultant so-
lution was then evaporated to dryness to give the titled compound
as a white powder (0.29 g, 61%); dH (300 MHz, CDCl3): 9.18 (s, 2H),
8.51 (d, J 8.4 Hz, 2H), 8.37 (dd, J 2.1, 8.1 Hz, 2H), 7.64 (d, J 9.0 Hz, 4H),
7.01 (d, J 9.0 Hz, 4H), 5.27 (t, J 9.0 Hz, 2H), 5.22e5.14 (m, 4H), 5.08 (t,
J 9.6 Hz, 2H), 5.05 (t, J 7.8 Hz, 2H), 4.95 (t, J 8.7 Hz, 2H), 4.57e4.53 (m,
4H), 4.40 (dd, J 4.5,12.6 Hz, 2H), 4.16 (dd, J 5.7,12.0 Hz, 2H), 4.07 (dd,
J 2.4, 12.3, 2H), 3.89 (t, J 8.7 Hz, 2H), 3.82e3.76 (m, 2H), 3.73e3.68
(m, 2H), 2.13 (s, 6H), 2.11 (s, 6H), 2.08 (s, 6H), 2.06 (s, 6H), 2.06 (s,
6H), 2.03 (s, 6H), 2.00 (s, 6H); dC (75 MHz, CDCl3þCD3OD): 170.907,
170.760, 170.554, 170.200, 169.995, 169.691, 169.436, 164.167,
157.237, 153.817, 148.506, 136.792, 133.627, 131.161, 122.299,
121.616, 117.572, 100.835, 99.264, 76.436, 73.016, 72.934, 72.588,
72.005, 71.701, 71.487, 67.829, 62.017, 61.663, 20.839, 20.716,
20.576; MALDI-TOF-MS, [MþNa]þ¼1685.37 (calcd 1685.49); nmax
1078 cmꢁ1
.
4.6. 5,50-Bis-(-N-(p-O-(2,3,6,2,3,4,6-hepta-O-acetyl-
b-malto-
syl)phenyl)-aminocarbonyl)-2,20-bipyridine (bpyMalAc)
To pAPMal (0.50 g, 0.68 mmol) and Et3N (2.0 ml) in THF
(50 ml), a THF solution (5.0 ml) containing bpyCOCl prepared from
0.08 g (0.33 mmol) of bpyCOOH was added and then, the resultant
mixture was stirred at the ambient temperature for 20 min. The
resultant reaction mixture was poured into iced water and diluted
with ethyl acetate. The organic layer was washed with 0.5 N HCl
aq and NaHCO3 saturated aqueous solution repeatedly. The or-
ganic layer was dried over anhydrous MgSO4, filtered and evapo-
rated to dryness. The residue was purified through column
chromatography packed with silica gel (eluent: CHCl3/MeOH¼50/
1, v/v) to give the title compound (0.25 g) in 46% yield (from
bpyCOOH) as a white powder; dH (300 MHz, CDCl3): 9.18 (s, 2H),
8.16 (d, J 8.1 Hz, 2H), 8.32 (dd, J 2.1, 8.1 Hz, 2H), 7.98 (s, 2H), 7.61 (d,
J 8.7 Hz, 4H), 7.03 (d, J 9.0 Hz, 4H), 5.45 (d, J 4.2 Hz, 2H), 5.42e5.30
(m, 4H), 5.12e5.03 (m, 6H), 4.88 (dd, J 4.2, 10.5 Hz, 2H), 4.51 (dd, J
2.7, 12.3 Hz, 2H), 4.27 (d, J 12.0 Hz, 2H), 4.27 (dd, J 9.6, 12.0 Hz, 2H),
4.11 (t, J 9.0 Hz, 2H), 4.04 (dd, J 2.4 and 12.0 Hz, 2H), 4.00e3.96 (m,
2H), 3.91e3.86 (m, 2H), 2.13 (s, 6H), 2.11 (s, 6H), 2.07 (s, 6H), 2.06
(s, 6H), 2.05 (s, 6H), 2.04 (s, 6H), 2.02 (s, 6H); dC (75 MHz, CDCl3):
170.579, 170.448, 170.250, 169.979, 169.691, 169.461, 163.583,
157.541, 153.924, 147.940, 136.052, 132.953, 130.668, 122.110,
121.452, 117.876, 98.903, 95.681, 75.293, 72.704, 72.400, 72.013,
70.048, 69.317, 68.635, 68.051, 20.930, 20.815, 20.675, 20.593;
MALDI-TOF-MS, [MþH]þ¼1663.56 (calcd 1663.49); nmax (KBr)
(KBr) 3371, 1747, 1513, 1227, 1049 cmꢁ1
.
4.9. 5,50-Bis-(-N-(p-O-(
2,20-bipyridine (bpyCel)
b-cellobiosyl)phenyl)-aminocarbonyl)-
To bpyCelAc (0.29 g, 0.17 mmol) in methanol/THF (1:1, 50 ml),
aqueous ammonia was added dropwise until pH value of the re-
sultant mixture became larger than 10. The resultant reaction
mixture was stirred at ambient temperature for 4 days. After con-
firming that the pH value of the reaction mixture was still larger
than 10, the resultant mixture was concentrated to form white
precipitate. The precipitate was retrieved through filtration and
dried over the filter paper overnight to give the title compound as
a white powder (0.16 g, >99%); dH (300 MHz, DMSO-d6þD2O): 9.22
(s, 2H), 8.59 (d, J 8.1 Hz, 2H), 8.49 (d, J 8.4 Hz, 2H), 7.69 (d, J 8.7 Hz,
4H), 7.10 (d, J 9.0 Hz, 4H), 4.96 (d, J 8.4 Hz, 2H), 4.34 (d, J 8.4 Hz, 2H),
3.82e3.03 (m, 24H); dC (75 MHz, DMSO-d6þD2O): 164.446,157.089,
154.516, 149.328, 137.622, 133.265, 131.580, 122.833, 121.641,
3362, 1749, 1511, 1233, 1051 cmꢁ1
.
4.7. 5,50-Bis-(-N-(p-O-(
2,20-bipyridine (bpyMal)
b-maltosyl)phenyl)-aminocarbonyl)-
To bpyMalAc (0.25 g, 0.15 mmol) in methanol/THF (1:1, 50 ml),
aqueous ammonia was added dropwise until pH value of the re-
sultant mixture became larger than 10. The resultant reaction
mixture was stirred at ambient temperature for overnight. After
confirming that the pH value of the reaction mixture was still larger