1.76–1.48 {m, 6H, OCH2(CH2)2CH2NCH2CH2(CH2)3CH3},
1.33–1.20 {m, 6H, NCH2CH2(CH2)3CH3}, 0.92–0.85 {m, 3H,
NCH2CH2(CH2)3CH3}. 13C NMR (CDCl3) d 156.53 (q, J = 15.6
Hz), 139.05, 139.02, 138.99, 138.97, 138.74, 138.73, 138.64, 138.58,
138.45, 138.43, 138.28, 138.24, 138.01, 128.33, 128.30, 128.25,
128.23, 128.20, 128.17, 128.10, 128.01, 127.97, 127.92, 127.79,
127.76, 127.72, 127.68, 127.66, 127.64, 127.52, 127.51, 127.48,
127.43, 127.40, 127.37, 127.29, 127.05, 127.04, 116.55 (q, J =
288.7 Hz), 103.46, 103.44, 102.75, 102.73, 82.93, 82.46, 81.68,
79.88, 76.65, 75.33, 75.18, 75.17, 75.08, 75.06, 74.91, 74.65, 73.50,
73.47, 73.33, 73.01, 72.91, 72.89, 72.48, 69.17, 68.97, 68.28, 68.23,
67.99, 47.46, 47.43, 47.22, 47.20, 46.82, 46.52, 31.38, 31.25, 28.59,
26.94, 26.77, 26.70, 26.38, 26.15, 25.57, 23.68, 22.45, 13.95, 13.91.
Anal. Calcd for C73H84F3NO12: C, 71.61; H, 6.91; N, 1.14. Found:
C, 71.54; H, 6.89; N, 1.26.
OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 1.26–1.18 {m, 6H,
OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 0.79 {br s, 3H
OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}. 13C NMR (CD3OD) d
157.88 (q, J = 35.0 Hz), 118.08 (q, J = 287.2 Hz), 105.11, 105.08,
99.96, 99.93, 80.99, 80.90, 77.08, 74.83, 74.79, 73.48, 73.47, 73.22,
73.17, 72.55, 72.17, 72.12, 70.29, 68.71, 68.56, 62.50, 61.87, 61.84,
48.09, 47.99, 32.62, 32.52, 29.71, 27.75, 27.55, 27.52, 27.29, 26.69,
24.78, 23.61, 23.60, 14.34, 14.31. Anal. Calcd for C24H42F3NO12:
C, 48.56; H, 7.13; N, 2.36. Found: C, 48.48; H, 7.20; N, 2.41.
N-Hexyl-4-aminobutyl 4-O-b-D-galactopyranosyl-
b-D-glucopyranoside 1b
A MeOH (0.20 mL) solution of compound 7b (10 mg, 20.5 mmol)
containing NaOMe (0.16 mL, 1 M in MeOH) was stirred for
5 h at 25 ◦C. After evaporation of the solvent, the residue was
applied to a SepPak C–18 column (H2O to MeOH) to obtain 1b
(8.0 mg, 89%): [a]D +3.9◦ (c 1.36 in H2O); IR nmax (ATR)/cm-1
25
N-Hexyl-N-trifluoroacetyl-4-aminobutyl
4-O-b-D-galactopyranosyl-b-D-glucopyranoside 7b
1
3356 (OH); H NMR (CD3OD): d 4.36 (d, 1H, J1¢,2¢ = 7.6 Hz,
H–1¢), 4.29 (d, 1H, J1,2 = 7.8 Hz, H–1), 3.93–3.90 {m, 1H,
A mixture of compound 6b (37 mg, 30.6 mmol) and 20%
Pd(OH)2/C (ca. 5 mg) in EtOH (1 mL) was stirred for 20 h
under a H2 atmosphere. The reaction mixture was filtered,
and the filtrate was concentrated in vacuo to afford the de-O-
OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 3.89 (dd, 1H, J5,6a =
2.4 Hz, J6a,6b 12.1 Hz, H–6a), 3.84 (dd, 1H, J5,6b = 4.2 Hz, H–6b),
3.81 (d, 1H, J3¢,4¢ = 2.9 Hz, H–4¢), 3.78 (dd, 1H, J5¢,6¢a = 7.6 Hz,
J6¢a,6¢b = 11.5 Hz, H–6¢a), 3.69 (dd, 1H, J5¢,6¢b = 4.6 Hz, H–6¢b), 3.61–
3.53 {m, 4H, H–2¢,4,5¢, OCH2(CH2)2CH2NCH2CH2(CH2)3CH3},
3.52 (t, 1H, J2,3 = J3,4 = 8.9 Hz, H–3), 3.84 (dd, 1H, J2¢,3¢ = 9.8 Hz,
H–3¢), 3.40 (ddd, 1H, J4,5 = 9.4 Hz, H–5), 3.24 (dd, 1H, H–2), 2.66–
2.54 {m, 4H, OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 1.69–
1.49 {m, 6H, OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 1.39–1.28
{m, 6H, OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 0.95–0.89 {m,
3H OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}.13C NMR (CDCl3)
d 105.07, 104.23, 80.51, 77.09, 76.45, 76.44, 74.78, 74.75, 72.55,
70.51, 70.29, 62.71, 62.50, 61.83, 50.56, 50.20, 49.62, 32.91, 30.78,
30.06, 28.40, 28.11, 26.66, 23.67, 14.40. HRMS (ESI) m/z Calcd
for [C22H43NO11Na]+: 520.2734. Found: 520.2729.
benzyl product 7b (13 mg, 72%): Rf 0.20 (EtOAc:MeOH = 3:1);
◦
[a]D -4.5 (c 1.03 in MeOH); m.p. 151–154 ◦C (crystallized
26
from EtOH); IR nmax (ATR)/cm-1 3371 (OH), 1682 (C O);
=
1H NMR (CD3OD): d 4.36 (d, 1H, J1¢,2¢ = 7.6 Hz, H–1¢),
4.29 (d, 1H, J1,2 = 7.9 Hz, H–1), 3.95–3.81 {m, 3H, H–6a,6b,
OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 3.81 (d, 1H, J3¢,4¢
=
3.1 Hz, H–4¢), 3.78 (dd, 1H, J5¢,6¢a = 7.6 Hz, J6¢a,6¢b = 11.5 Hz,
H–6¢a), 3.69 (dd, 1H, J5¢,6¢b = 4.6 Hz, H–6¢b), 3.59–3.38 {m,
11H, H–2¢,3,3¢,4,5,5¢, OCH2(CH2)2CH2NCH2CH2(CH2)3CH3},
3.24 (dd, 1H, J2,3
=
8.8 Hz, H–2), 1.78–1.50 {m,
6H, OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 1.37–1.29 {m,
6H, OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 0.92 {m, 3H,
OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}. 13C NMR (CD3OD) d
157.87 (q, J = 35.0 Hz), 118.09 (q, J = 286.9 Hz), 105.09, 104.20,
104.17, 80.70, 80.61, 77.08, 76.49, 76.44, 74.80, 74.74, 74.73,
72.55,70.28, 70.21, 70.08, 62.48, 61.95, 61.90, 48.12, 47.94, 32.63,
32.54, 29.71, 27.87, 27.77, 27.71, 27.54, 27.31, 26.58, 24.62, 23.62,
23.61, 14.36, 14.33. Anal. Calcd for C24H42F3NO12: C, 48.56; H,
7.13; N, 2.36. Found: C, 48.43; H, 7.09; N, 2.54.
N-Hexyl-4-aminobutyl 4-O-b-D-galactopyranosyl-
a-D-glucopyranoside 1a
Compound 1a was obtained from 7a in the same manner
as 1b was obtained from 7b (quant.): [a]D +102.1◦ (c 0.65
25
in H2O); IR nmax (ATR)/cm-1 3332 (OH); 1H NMR (D2O):
d 4.84 (d, 1H, J1,2 = 3.2 Hz, H–1), 4.38 (d, 1H, J1¢,2¢
7.8 Hz, H–1¢), 3.85–3.56 {m, 12H, H–3,3¢,4,4¢,5,5¢,6a,6¢a,6b,6¢b,
OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 3.54 (dd, 1H, J2,3
=
=
9.6 Hz, H–2), 3.47 (dd, 1H, J2¢,3¢ = 8.6 Hz, H–2¢), 2.83–
2.75 {m, 4H, OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 1.66–1.47
{m, 4H, OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 1.30–1.18 {m,
8H, OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 0.80 {br t, 3H,
OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}. 13C NMR (CDCl3) d
105.09, 99.93, 80.98, 77.10, 74.84, 73.49, 73.22, 72.58, 72.15,
70.30, 68.92, 62.51, 61.89, 50.59, 50.25, 32.89, 30.01, 28.23, 28.08,
26.91, 23.66, 14.38. HRMS (ESI) m/z Calcd for [C22H43NO11Na]+:
520.2734. Found: 520.2730.
N-Hexyl-N-trifluoroacetyl-4-aminobutyl
4-O-b-D-galactopyranosyl-a-D-glucopyranoside 7a
Compound 7a was obtained from 6a in the same manner as
7b was obtained from 6b (97%): Rf 0.18 (EtOAc:MeOH =
3:1); [a]D +56.7◦ (c 1.19 in MeOH); IR nmax (ATR)/cm-1 3345
26
1
=
(OH), 1682 (C O); H NMR (CD3OD) d 4.78 (d, 1H, J1,2
=
3.7 Hz, H–1), 4.35 (d, 1H, J1¢,2¢ = 7.6 Hz, H–1¢), 3.88–3.65,
3.60–3.40 {each m, 18H, H–2,2¢,3,3¢,4,4¢,5,5¢,6a,6¢a,6b,6¢b,
OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 1.80–1.57 {m, 6H,
OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 1.38–1.28 {m, 6H,
OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 0.93-0.90 {m, 3H
OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}. 1H NMR (D2O): d
4.84 (d, 1H, J1,2 = 3.8 Hz, H–1), 4.38 (d, 1H, J1¢,2¢ = 7.7 Hz,
H–1¢), 3.89–3.36 {m, 18H, H–2,2¢,3,3¢,4,4¢,5,5¢,6a,6¢a,6b,6¢b,
OCH2(CH2)2CH2NCH2CH2(CH2)3CH3}, 1.70–1.50 {m, 6H,
N-Hexyl-N-{4,4-difluoro-5,7-dimethyl-4-bora-3a,4a-diaza-s-
indacene-3-propanoyl}-4-aminobutyl 4-O-b-D-galactopyranosyl-
b-D-glucopyranoside 9
DMT-MM (23.4 mg, 84.6 mmol) and H2O (0.50 mL) were added
to a solution of 1b (12.4 mg, 24.9 mmol) and BODIPY–FL C–3
acid (14.6 mg, 50.0 mmol) in THF (1.99 mL). After the mixture was
This journal is
The Royal Society of Chemistry 2009
Org. Biomol. Chem., 2009, 7, 4726–4733 | 4731
©