964
S. Hanashima et al. / Carbohydrate Research 344 (2009) 959–965
Glc-H-4, J4,5 = 9.1 Hz), 3.61 (3H, s, Glc-OCH3), 3.60 (1H, dd, Glc-H-
6.24 (1H, d, Neu-NH, J5,NH = 10.3 Hz), 5.44 (1H, dd, Neu-H-7,
J6,7 = 2.3 Hz, J7,8 = 2.7 Hz), 5.36 (1H, ddd, Neu-H-4, J3ax,4 = 11.5 Hz,
J3eq,4 = 4.8 Hz, J4,5 = 9.4 Hz), 5.05 (1H, ddd, Neu-H-8, J8,9 = 2.5 Hz,
0
2), 3.60 (1H, ddd, Glc-H-5, J5,6 = 1.4 Hz, J5,6 = 1.7 Hz), 3.56 (1H,
dd, Glc-H-6, J6,6 = 11.2 Hz), 3.43 (1H, dd, Glc-H-60), 2.61 (1H, dd,
0
0
Neu-H-3eq, J3ax,3eq = 12.8 Hz), 2.11 (3H, s), 2.07 (3H, s), 1.96 (3H,
s), 1.94 (3H, s), 1.84 (3H, s), 1.88 (1H, dd, Neu-H-3ax); 13C NMR
(150 MHz, CDCl3): d 171.0, 170.6, 170.2, 169.9, 169.6, 168.0,
167.6, 155.3, 151.6, 138.5, 138.3, 138.3, 128.4, 128.4, 128.4,
128.3, 128.2, 128.2, 128.0, 127.9, 127.8, 127.8, 127.8, 127.7,
127.6, 118.4, 114.5, 102.8, 98.8, 84.5, 81.9, 75.8, 75.0, 75.0, 74.0,
72.2, 68.2, 68.0, 67.0, 63.6, 62.8, 62.1, 55.7, 52.7, 49.4, 38.2, 21.2,
20.8, 20.7, 20.7, 20.6; HRESIMS: calcd for C56H65NO21Na, m/z
[M+Na]+, 1110.3947; found, 1110.3965. Compound 12b: Rf 0.2
J8,9 = 5.0 Hz), 4.97, 4.75 (2H, each d, Glc-PhCH2, JAB = 11.0 Hz),
4.86 (1H, d, Glc-H-1, J1,2 = 6.7 Hz), 4.84, 4.82 (2H, each d, Glc-
PhCH2, JAB = 10.1 Hz), 4.76, 4.74 (2H, each d, Glc-PhCH2,
JAB = 11.2 Hz), 4.59 (1H, dd, Neu-H-6, J5,6 = 11.4 Hz), 4.53, 4.48
(2H, each d, Neu-PhCH2, JAB = 11.9 Hz), 4.39 (1H, dd, Neu-H-9,
J9,9 = 12.6 Hz), 4.13 (1H, ddd, Neu-H-5), 3.92 (1H, dd, Neu-H-90),
0
3.84, 3.77 (2H, each d, Neu-COCH2, JAB = 15.3 Hz), 3.80 (1H, dd,
Glc-H-6, J5,6 = 4.0 Hz, J6,6 = 9.7 Hz), 3.77 (1H, ddd, Glc-H-5,
J4,5 = 9.8 Hz,
0
0
J5,6 = 4.8 Hz),
3.74
(1H,
dd,
Glc-H-3,
(1:2 hexane–EtOAc); ½a D25
ꢁ
þ 15 (c 1.1, CHCl3); 1H NMR (600 MHz,
J2,3 = J3,4 = 8.9 Hz), 3.73 (3H, s, Glc-OCH3), 3.66 (1H, dd, Glc-H-2),
3.62 (3H, s, Neu-COOCH3), 3.55 (1H, dd, Glc-H-4), 3.44 (1H, dd,
H-60), 2.65 (1H, dd, Neu-H-3eq, J3ax,3eq = 12.7 Hz), 2.08, 2.00, 1.94,
1.84 (12H, each s, Neu-OCOCH3 ꢂ 4); 13C NMR (150 MHz, CDCl3):
d 170.6, 170.4, 170.1, 170.0, 169.8, 167.8, 155.3, 151.6, 138.6,
138.3, 138.3, 136.8, 128.6, 128.4, 128.4, 128.4, 128.4, 128.3,
128.2, 128.1, 128.1, 127.8, 127.8, 127.7, 127.6, 118.4, 114.5,
104.4, 102.8, 98.7, 84.5, 81.9, 77.1, 77.1, 76.9, 75.6, 75.1, 75.0,
74.0, 73.5, 72.6, 72.1, 69.2, 69.0, 67.6, 66.9, 63.5, 62.1, 55.7, 52.7,
48.5, 38.1, 21.2, 20.8, 20.8, 20.6, –11.1; HRESIMS: calcd for
C61H69NO20Na, m/z [M+Na]+, 1158.4311; found, 1158.4330. Com-
CDCl3): d 7.35–7.26 (15H, m, PhH), 7.03–7.01, 6.84–6.83 (4H, each
m, PhH), 5.84 (1H, d, Neu-NH, J5,NH = 10.0 Hz), 5.27 (1H, ddd, Neu-
H-4, J3ax,4 = 10.9 Hz, J3eq,4 = 4.8 Hz, J4,5 = 10.8 Hz), 5.23 (1H, dd,
Neu-H-7, J6,7 = 2.2 Hz, J7,8 = 3.5 Hz), 5.13 (1H, ddd, Neu-H-8,
0
J8,9 = 2.2 Hz, J8,9 = 8.1 Hz), 4.96, 4.76 (2H, each d, Glc-PhCH2,
JAB = 10.8 Hz), 4.87, 4.77 (2H, each d, Glc-PhCH2, JAB = 11.0 Hz),
4.86 (1H, d, Glc-H-1, J1,2 = 6.7 Hz), 4.82, 4.66 (2H, each d, Glc-
0
PhCH2, JAB = 10.8 Hz), 4.77 (1H, dd, Neu-H-9, J9,9 = 10.8 Hz), 4.43,
4.14 (2H, each d, Neu-COCH2, JAB = 15.3 Hz,), 4.16 (1H, dd, Neu-H-
6, J5,6 = 10.3 Hz), 4.12 (1H, dd, Glc-H-3, J2,3 = J3,4 = 10.3 Hz), 4.14
(1H, ddd, Neu-H-5), 4.01 (1H, dd, Neu-H-90), 3.80 (1H, dd, Glc-H-
pound 13b: Rf 0.09 (1:1 hexane–EtOAc); ½a D25
ꢀ 8:5 (c 1.1, CHCl3);
ꢁ
0
6, J5,6 = 2.4 Hz, J6,6 = 11.3 Hz), 3.74 (1H, ddd, Glc-H-5, J4,5 = 8.8 Hz,
1H NMR (600 MHz, CDCl3): d 7.33–7.25 (20H, m, PhH), 7.01–7.00,
6.84–6.83 (4H, each m, PhH), 6.42 (1H, d, Neu-NH, J5,NH = 9.8 Hz),
5.36 (1H, dd, Neu-H-7, J6,7 = 1.7 Hz, J7,8 = 3.8 Hz), 5.32 (1H, ddd,
Neu-H-4, J3ax,4 = 11.3 Hz, J3eq,4 = 4.8 Hz, J4,5 = 10.6 Hz), 5.20 (1H,
0
J5,6 = 3.6 Hz), 3.72 (3H, s, Glc-OCH3), 3.67 (1H, dd, Glc-H-2), 3.64
(1H, dd, Glc-H-4), 3.57 (3H, s, Neu-COOCH3), 3.50 (1H, ddd, Glc-
H-60), 2.41 (1H, dd, Neu-H-3eq, J3ax,3eq = 12.9 Hz), 2.18, 2.14, 2.03,
2.02, 1.91 (15H, each s, Neu-OCOCH3 ꢂ 5); 13C NMR (150 MHz,
CDCl3): d 171.0, 170.6, 170.1, 170.0, 169.7, 167.6, 166.9, 155.5,
151.5, 138.4, 138.2, 138.1, 128.4, 128.4, 128.1, 127.9, 127.8,
127.8, 127.8, 127.8, 127.8, 127.7, 118.5, 114.7, 103.3, 97.9, 84.4,
82.1, 76.7, 75.7, 75.2, 74.9, 73.8, 71.8, 71.5, 68.3, 68.2, 62.5, 61.4,
55.6, 52.6, 48.8, 37.3, 20.8, 20.8, 20.7, 20.6; HRESIMS: calcd for
C56H65NO21Na, m/z [M+Na]+, 1100.3947; found, 1110.3983.
0
ddd, Neu-H-8, J8,9 = 1.5 Hz, J8,9 = 7.9 Hz), 5.00, 4.80 (2H, each d,
Glc-PhCH2, JAB = 10.8 Hz), 4.93, 4.80 (2H, each d, PhCH2,
JAB = 11.0 Hz), 4.90 (1H, d, Glc-H-1, J1,2 = 7.4 Hz), 4.88, 4.73 (2H,
each d, PhCH2, JAB = 11.0 Hz), 4.79 (1H, dd, Neu-H-6,
J5,6 = 10.5 Hz), 4.52, 4.47 (2H, each d, Neu-PhCH2, JAB = 12.2 Hz),
0
4.22 (1H, ddd, Neu-H-5), 4.20 (1H, dd, Neu-H-9, J9,9 = 12.5 Hz),
4.09 (1H, dd, Neu-H-90), 3.85 (1H, dd, Glc-H-6, J5,6 = 2.4 Hz,
0
J6,6 = 7.4 Hz), 3.84, 3.78 (2H, each d, Neu-COCH2, JAB = 15.3 Hz),
4.10. 4-Methoxyphenyl (methyl 4,7,8,9-tetra-O-acetyl-5-(2-
benzyloxy)acetamido-3,5-dideoxy-D-glycero-a-D-galacto-2-
3.79 (1H, dd, Glc-H-3, J2,3 = J3,4 = 10.5 Hz), 3.75 (1H, dd, Glc-H-4,
J4,5 = 9.6 Hz), 3.75 (3H, s, Glc-OCH3), 3.72 (1H, dd, Glc-H-2), 3.71
0
nonulopyranosylonate)-(2?6)-2,3,4-tri-O-benzyl-b-
D
-
(1H, ddd, Glc-H-5, J5,6 = 7.4 Hz), 3.61 (3H, s, Neu-COOCH3), 3.55
glucopyranoside (13)
(1H, dd, H-60), 2.56 (1H, dd, Neu-H-3eq, J3ax,3eq = 13.0 Hz), 2.12,
2.00, 1.99, 1.89 (12H, each s, Neu-OCOCH3 ꢂ 4), 1.90 (1H, dd,
Neu-H-3ax); 13C NMR (150 MHz, CDCl3): d 170.6, 170.3, 170.2,
170.1, 169.9, 166.9, 155.4, 151.5, 138.4, 138.3, 138.2, 136.8,
128.5, 128.4, 128.4, 128.4, 128.4, 128.4, 128.3, 128.1, 128.1,
128.0, 128.0, 127.9, 127.7, 127.7, 127.6, 118.6, 114.6, 103.2, 98.1,
84.4, 82.1, 76.9, 75.7, 75.1, 74.8, 73.8, 73.2, 71.6, 71.5, 68.9, 68.8,
68.3, 62.5, 61.8, 55.5, 52.6, 48.1, 37.3, 20.9, 20.8, 20.8, 20.7; HRE-
SIMS: calcd for C56H65NO21Na, m/z [M+Na]+, 1158.4284; found,
1158.4311.
4.10.1. Conditions in CH2Cl2
To a solution of donor 2 (44 mg, 0.052 mmol) and acceptor 11
(19 mg, 0.034 mmol) in CH2Cl2 (5 mL) added 4 Å MS was stirred
for 15 min at –78 °C. TMSOTf (1.5 lL, 0.0078 mmol) was then
added. After stirring for 10 min at –78 °C under an atmosphere of
argon, the reaction mixture was neutralized with excess Et3N
and filtered through Celite. The filtrate was concentrated, and the
crude product was purified by silica gel column chromatography
(1:1 hexane–EtOAc) to give 13 (35 mg, 0.031 mmol, 90%,
4.11. Methyl 5-(2-acetoxy)acetamido-4,7,8,9-tetra-O-acetyl-3,5-
a/b = 1:10).
dideoxy-D-glycero-a-D-galacto-2-nonulopyranosylonate-(2?3)-
4,6-di-O-benzyl-
D
-galactal (15)
4.10.2. Conditions in EtCN
To a solution of donor 2 (45 mg, 0.053 mmol) and acceptor 11
(20 mg, 0.036 mmol) in EtCN (5 mL) added 4 Å MS was stirred for
To a solution of donor 1 (47 mg, 0.059 mmol) and acceptor 14
(23 mg, 0.070 mmol) in EtCN (5 mL) added 4 Å MS was stirred for
15 min at –78 °C. TMSOTf (1.5
lL, 0.0078 mmol) was then added.
15 min at –78 °C. TMSOTf (1% in EtCN, 230 lL, 12 lmol) was then
After stirring for 10 min at –78 °C under an atmosphere of argon,
the reaction mixture was neutralized with excess Et3N and filtered
through Celite. The filtrate was concentrated, and the crude prod-
uct was purified by silica gel column chromatography (1:1 hex-
added. After stirring for 10 min at –78 °C under an atmosphere of
argon, the mixture was neutralized with excess Et3N and filtered
through Celite. The filtrate was concentrated, and the crude prod-
uct was purified by silica gel column chromatography (1:2 hex-
ane–EtOAc) to give 15 (31 mg, 0.036 mmol, 61%). Compound 15:
ane–EtOAc) to give 13 (31 mg, 0.027 mmol, 76%,
a
/b = 8:1).
Compound 13
a
: Rf 0.11 (1:1 hexane–EtOAc); ½a D25
ꢁ
ꢀ 11 (c 0.7,
Rf 0.17 (1:2 hexane–EtOAc); ½a D25
ꢁ
ꢀ 32 (c 2.4, CHCl3); 1H NMR
CHCl3); IR (KBr, neat):
m
1455 cmꢀ1 (C=C), 1746 cmꢀ1 (COO),
(600 MHz, CDCl3): d 7.40–7.24 (10H, m), 6.37 (1H, dd, J = 1.5,
6.2 Hz), 5.89 (1H, d, J = 9.8 Hz), 5.40 (1H, ddd, J = 2.6, 5.7, 8.4 Hz),
5.25 (1H, dd, J = 2.1, 8.2 Hz), 5.01 (1H, ddd, J = 4.5, 7.6, 10.3 Hz),
2927 cmꢀ1 (NH), 3368 cmꢀ1 (OH); 1H NMR (600 MHz, CDCl3): d
7.46–7.29 (20H, m, PhH), 6.96–6.94, 6.79–6.77 (4H, each m, PhH),