398
S. Sarkar, S. J. Sucheck / Carbohydrate Research 346 (2011) 393–400
22.68, (4C, CH3–CO), 21.07, 20.99, 20.95, 20.87 (4C, CH3–CO0),
H-6e), 4.01 (d, 1H, J = 8.4 Hz, H-1), 3.93 (t, 1H, J = 10.8 Hz, H-3),
15.48, 14.93 (2C, O–CH2–CH3, O–CH2–CH0 ); HRMS: calcd for
3.85 (m, 1H, O–CHa–CH0 ), 3.80, 3.78 (2s, 6H, O–CH3), 3.59 (m, 1H,
3
3
C
27H33NO9Na, m/z [M+Na]+ 538.2053; found, m/z 538.2039.
O–CHa–CH3), 2.76 (s, 2H, N–CH2), 2.54 (m, 1H, O–CHb–CH3), 2.35
(m, 1H, O–CHb–CH0 ), 2.13, 2.10, 2.07, 2.06, 2.04, 2.03, 2.02, 1.99
3
0
(8s, 24H, CH3–CO, CH3–CO0), 1.22 (t, 3H, J = 7.2 Hz, O–CH2–CH3 ),
1.04 (t, 3H, J = 7.2 Hz, O–CH2–CH3); 13C NMR (100 MHz, CDCl3): d
172.99 (2), 170.99 (2), 170.90, 170.16 (2), 169.88 (8C, C-aromatic,
C0-aromatic), 158.99 (1C, O–C-aromatic), 147.69 (1C, O–C0-aro-
matic), 133.76, 132.87, 130.58, 130.13, 130.06, 129.21, 128.76,
128.41, 114.18, 113.96 (10C, C-aromatic, C0-aromatic), 100.17,
99.57 (2C, C-1, C-10), 71.66, 71.44, 71.38, 70.90, 69.79, 69.61,
68.13, 65.91, 65.73, 65.52 (10C, C-4, C-40, C-3, C-30, C-2, C-20, C-6,
0
3.5. Synthesis of ethyl 3,4,6-tri-O-acetyl-2-deoxy-2-(N-(4-
methoxybenzyl)acetamido)-b- -glucopyranoside (11)
D
3.5.1. p-Methylphenyl 2-deoxy-2-(4-methoxybenzylamino)-1-
thio-b- -glucopyranoside (9)
p-Methylphenyl 2-amino-2-deoxy-1-thio-b-
D
D
-glucopyranoside
(4) (500 mg, 1.75 mmol) was condensed with 4-methoxybenzalde-
hyde (0.24 mL, 1.97 mmol), and the product was subjected to
reductive amination with sodium triacetoxyborohydride (447 mg,
1.97 mmol) according to procedures described in Section 3.2.1 to
afford 9 as a white foam (538 mg, 76%). 1H NMR (600 MHz,
CD3OD): d 7.45 (d, 2H, J = 7.8 Hz, ArH), 7.29 (d, 2H, J = 9 Hz, ArH),
7.14 (d, 2H, J = 7.8 Hz, ArH), 6.89 (d, 2H, J = 9 Hz, ArH), 4.64 (d,
1H, J = 10.2 Hz, H-1), 3.97 (d, 2H, J = 12 Hz, N–CH2), 3.92 (d, 1H,
J = 12 Hz, H-5), 3.85 (dd, 1H, J = 2.4, 12 Hz, H-6a), 3.78 (s, 3H, O–
CH3), 3.67 (q, 1H, J = 5.8 Hz, H-6e), 3.46 (t, 1H, J = 9 Hz, H-3), 3.28
(m, 1H, H-4), 2.58 (t, 1H, J = 10.2 Hz, H-2), 2.32 (s, 3H, Ar-CH3);
13C NMR (100 MHz, CD3OD): d 160.73, 139.09, 133.27 (2), 132.49,
131.25 (2), 131.13, 130.84 (2), 115.06 (2) (12C, C-aromatic),
89.19 (1C, C-1), 82.32, 78.24, 71.97, 63.20, 62.94 (5C, C-2, C-3, C-
4, C-6, C-5), 55.81 (1C, O–CH3), 53.21 (1C, N–CH2), 21.27 (1C, Ar-
CH3); HRMS: calcd for C21H28NO5S m/z [M+H]+ 406.1688; found
m/z 406.1684.
C-60, C-5, C-50), 61.41, 62.12 (2C, O–CH2–CH3, O–CH2–CH0 ), 59.07,
3
56.13 (2C, N–CH2, N–CH0 ), 55.52, 43.92 (2C, O–CH3, O–CH0 ),
2
3
22.63, 21.56, 21.34, 21.06, 20.97, 20.94, 20.89, 20.83 (8C, CH3–
CO, CH3–CO0), 15.38, 15.03 (2C, O–CH2–CH3, O–CH2–CH3); HRMS:
calcd for C24H33NO10Na m/z [M+Na]+ 518.2002; found m/z
518.1993.
3.6. Synthesis of ethyl 3,4,6-tri-O-acetyl-2-deoxy-2-[acetyl(3,4-
dimethoxybenzyl)amino]-b-D-glucopyranoside (14)
3.6.1. p-Methylphenyl 2-deoxy-2-(3,4-dimethoxybenzylamino)-
1-thio-b- -glucopyranoside (12)
p-Methylphenyl 2-amino-2-deoxy-1-thio-b-
D
D-glucopyranoside
(4) (500 mg, 1.75 mmol) was condensed with 3,4-dimethoxybenz-
aldehyde (326 mg, 1.96 mmol) and subjected to reductive amina-
tion with sodium triacetoxyborohydride (443 mg, 1.96 mmol)
according to procedures described in Section 3.2.1 to afford 12 as
a white foam (419 mg, 55%). 1H NMR (600 MHz, CD3OD): d 7.44
(d, 2H, J = 8.4 Hz, ArH), 7.13 (d, 2H, J = 8.4 Hz, ArH), 7.02 (s, 1H,
ArH), 6.90 (s, 1H, ArH), 4.65 (d, 1H, J = 10.2 Hz, H-1), 4.00, 3.92
(2d, 2H, J = 12.3 Hz, N–CH2), 3.85 (m, 1H, H-5), 3.83, 3.81 (2s, 6H,
O–CH3), 3.67 (dd, 2H, J = 5.4, 12 Hz, H-6), 3.48 (t, 1H, J = 9 Hz, H-
3), 3.29 (m, 1H, H-4), 2.59 (t, 1H, J = 10.2 Hz, H-2), 2.31 (s, 3H,
Ar-CH3); 13C NMR (100 MHz, CD3OD): d 150.56, 150.01, 139.04,
133.16 (2), 131.11, 130.83 (3), 122.57, 113.85, 112.87 (12C, C-aro-
matic), 89.13 (1C, C-1), 82.28, 78.23, 71.91, 62.91 (4C, C-2, C-3, C-4,
C-6), 52.57, 56.51 (2C, O–CH3), 53.38 (1C, C-5), 21.27 (1C, Ar-CH3);
HRMS: calcd for C22H29NO6SNa m/z [M+Na]+ 458.1613; found m/z
458.1605.
3.5.2. p-Methylphenyl 3,4,6-tri-O-acetyl-2-deoxy-2-[acetyl(4-
methoxybenzyl)amino]-1-thio-b-D-glucopyranoside (10)
p-Methylphenyl 2-deoxy-2-(4-methoxybenzylamino)-1-thio-b-
-glucopyranoside (9) (538 mg, 1.33 mmol) was acetylated accord-
D
ing to procedures described in Section 3.2.2 to afford 10 as a white
foam that was a mixture of two rotational isomers (0.132 mg, 94%).
1H NMR (600 MHz, CDCl3): d 7.37 (d, 3H, J = 7.8 Hz, ArH), 7.25 (m,
2H, ArH), 6.86 (d, 2H, J = 7.8 Hz, ArH), 6.71 (m, 1H, ArH), 6.15 (t, 1H,
J = 9 Hz, H-3), 5.89 (d, 1H, J = 9.6 Hz, H-1), 5.36 (t, 1H, J = 9.6 Hz, H-
30), 5.05 (t, 1H, J = 9.3 Hz, H-40), 4.98 (m, 1H, H-60), 4.90 (t, 1H,
J = 8.4 Hz, H-4), 4.57 (d, 1H, J = 10.2 Hz, H-10), 4.20 (dd, 1H, J = 5.4,
12.3 Hz, H-6a), 4.10 (m, 1H, H-60), 4.05 (t, 1H, J = 10.8 Hz, H-20),
4.01 (m, 1H, H-5), 3.79 (s, 3H, O–CH3), 3.71 (s, 3H, O–CH0 ), 3.63
3
(m, 1H, H-6e), 3.52 (m, 1H, H-50), 3.18 (t, 1H, J = 9.9 Hz, H-2),
2.96 (s, 2H, N–CH2), 2.82 (s, 2H, N–CH0 ), 2.33, 2.30, 2.21, 2.13 (4s,
3.6.2. p-Methylphenyl 3,4,6-tri-O-acetyl-2-deoxy-2-[acetyl(3,4-
2
12H, CH3–CO), 2.07, 2.03, 2.00, 1.96 (4s, 12H, CH3–CO0), 1.68 (s,
dimethoxybenzyl)amino]-1-thio-b-
p-Methylphenyl 2-deoxy-2-(3,4-dimethoxybenzylamino)-1-
thio-b- -glucopyranoside (12) (250 mg, 0.574 mmol) was acety-
D-glucopyranoside (13)
3H, Ar-CH3), 1.24 (s, 3H, Ar-CH0 ); 13C NMR (150 MHz, CDCl3): d
3
172.32, 172.21, 170.56, 170.68 (4C, CH3–CO), 170.04, 169.97,
169.85, 169.56 (4C, CH3–CO0), 159.49, 158.91 (2C, O–C-aromatic,
O–C0-aromatic), 132.46, 129.96, 129.91, 129.87, 129.81, 129.69,
129.47, 128.60, 128.34, 128.02 (10C, C-aromatic), 86.45, 84.91
(2C, C-1, C-10), 77.44, 77.23, 77.02, 75.37, 71.52, 71.18, 69.85,
69.44, 63.82, 62.54 (10C, C-3, C-30, C-2, C-20, C-4, C-40, C-6, C-60,
C-5, C-50), 61.43, 56.07 (2C, O–CH3, O–CH03), 55.41, 55.21 (2C, N–
CH2, N–CH0 ), 23.78, 22.55 (2C, Ar-CH3, Ar-CH0 ), 21.24 (2), 20.97,
D
lated according to procedures described in Section 3.2.2 to afford
13 as a white foam that was a mixture of two rotational isomers
(260 mg, 38%). 1H NMR (600 MHz, CDCl3): d = 7.37–6.53 (14H,
ArH), 6.11 (t, 1H, J = 9.3 Hz, H-3), 5.90 (d, 1H, J = 10.2 Hz, H-1),
4.89 (t, 1H, J = 9.6 Hz, H-4), 4.60, 4.48 (2d, 4H, J = 10.8 Hz, N–CH2,
N–CH02), 4.19 (dd, 1H, J = 5.4, 12.3 Hz, H-6a), 4.09 (dd, 1H, J = 1.8,
5.6 Hz, H-6e), 3.85, 3.84 (2s, 6H, O–CH3), 3.81, 3.76 (2s, 6H, O–
CH03), 3.63 (m, 1H, H-5), 3.17 (t, 1H, J = 9.6 Hz, H-2), 2.31, 2.28,
2.19, 2.13 (4s, 12H, CH3–CO), 2.05, 2.02, 2.00, 1.95 (4s, 12H, CH3–
CO0), 1.68 (s, 3H, Ar-CH3), 1.23 (s, 3H, Ar-CH03); 13C NMR
2
3
20.86 (2), 20.78, 20.75, 20.64 (8C, CH3–CO, CH3–CO0); HRMS: calcd
for C29H35NO9SNa m/z [M+Na]+ 596.1930; found m/z 596.1903.
3.5.3. Ethyl 3,4,6-tri-O-acetyl-2-deoxy-2-[acetyl(4-
(100 MHz, CDCl3): d 172.23, 172.15, 170.66, 170.03, 169.90,
methoxybenzyl)amino]-b-
p-Methylphenyl 3,4,6-tri-O-acetyl-2-deoxy-2-[acetyl(4-methoxy
benzyl)amino]-1-thio-b- -glucopyranoside (10) (220 mg,
0.384 mmol) was glycosylated with EtOH (43 L, 0.770 mmol)
D
-glucopyranoside (11)
169.76, 169.53 (8C, CH3–CO, CH3–CO0), 149.95, 149.91, 149.18,
148.39, 138.26, 138.06, 132.48, 132.12, 131.91, 130.50, 129.84,
129.64, 129.58, 129.33, 129.09, 128.44, 128.29, 120.89, 120.56,
111.34, 111.42, 111.19, 110.47, 110.26 (24C, C-aromatic, C0-aro-
matic), 86.36, 84.84 (2C, C-1, C-10), 77.55, 77.23, 76.91, 75.36,
71.66, 71.04, 69.48, 64.11, 62.48 (10C, C-3, C-30, C-2, C-20, C-4, C-
40, C-6, C-60, C-5, C-50), 56.45, 56.00 (4C, O–CH3, O–CH0 ), 55.60,
48.30 (2C, N–CH2, N–CH0 ), 29.75 (2C, Ar-CH3, Ar-CH03), 23.72,
D
l
according to procedures described in Section 3.2.3 to generate 11
as colorless oil that was a mixture of two rotational isomers
(59 mg, 31%). 1H NMR (600 MHz, CDCl3): d 7.37–6.86 (m, 8H,
ArH), 5.46 (t, 1H, J = 9.9 Hz, H-3), 5.08 (t, 1H, J = 9.6 Hz, H-4), 4.29
(dd, 1H, J = 4.8, 12.0 Hz, H-6a), 4.13 (dd, 1H, J = 1.8, 12.3 Hz,
2
3
22.64, 22.52, 21.53, 21.19, 20.80, 20.75, 20.57 (8C, CH3–CO,