Pilgrim and Murphy
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Analytical Data for r-Anomers of 1-14.33 Butyl 2,3,4,6-
tetra-O-acetyl-r-D-glucopyranoside 1r: IR (film) (cm-1) 2959,
1748, 1367, 1221, 1037; 1H NMR (CDCl3, 500 MHz) δ 5.50 (1H,
t, J = 9.8 Hz), 5.09 (1H, d, J = 3.7 Hz), 5.05 (1H, t, J = 9.8 Hz),
4.86 (1H, dd, J = 9.8 Hz, J = 3.7 Hz), 4.29 (1H, dd, J = 12.3 Hz,
J = 4.6 Hz), 4.15 (1H, dd, J = 12.3 Hz, J = 2.3 Hz), 4.04 (1H,
ddd, J = 10.2, J = 4.6 Hz, J = 2.3 Hz), 3.70 (1H, dt, J = 9.8 Hz,
J = 6.5 Hz), 3.45 (1H, dt, J = 9.8 Hz, J = 6.5 Hz), 2.18 (3H, s),
2.11 (3H, s), 2.08 (3H, s), 2.06 (3H, s), 1.59 (2H, m), 1.40 (2H, m),
0.94 (3H, t, J = 7.4 Hz); 13C NMR (CDCl3, 125 MHz) δ 170.7,
170.2, 170.1, 169.6, 95.6, 71.0, 70.3, 68.7, 68.4, 67.1, 62.0, 31.3,
20.7 (2s), 20.6, 19.2, 13.7; ESI-HRMS calcd for C18H28O10Na
427.1580, found m/z 427.1559 [M þ Na]þ.
s), 1.57 (2H, m), 1.36 (2H, m), 0.92 (3H, t, J = 7.4 Hz); 13C NMR
(CDCl3, 125 MHz) δ 170.2, 167.0, 169.8, 167.6, 96.4, 69.2, 69.0,
68.4, 67.8, 67.3, 52.7, 31.3, 20.7, 20.6 (2s), 19.2, 13.7; ESI-HRMS
calcd for C17H26O10Na 413.1424, found m/z 413.1431 [M þ Na]þ.
Butyl 2,3,4,6-tetra-O-benzoyl-r-D-glucopyranoside 7r: 1H
NMR (CDCl3, 500 MHz) δ 8.05 (2H, d, J = 7.5 Hz), 7.99
(2H, d, J = 7.5 Hz), 7.95 (2H, d, J = 7.3 Hz), 7.87 (2H, d, J =
7.4 Hz), 7.55 (1H, t, J = 7.4 Hz), 7.49 (2H, m), 7.41 (3H, t, J =
7.8 Hz), 7.36 (4H, m), 7.28 (2H, t, J = 7.7 Hz), 6.21 (1H, t, J =
9.8 Hz), 5.68 (1H, t, J = 9.8 Hz), 5.35 (1H, d, J = 3.7 Hz), 5.32
(1H, dd, J = 9.8 Hz, J = 3.7 Hz), 4.61 (1H, m), 4,48 (2H, m),
3.81 (1H, dt, J = 9.8 Hz, J = 6.5 Hz), 3.51 (1H, dt, J = 9.8 Hz,
J = 6.6 Hz), 1.60 (2H, m), 1.35 (2H, m), 0.83 (3H, t, J = 7.4 Hz);
13C NMR (CDCl3, 125 MHz) δ 166.4, 165.9, 165.8, 165.4, 133.4
(2s), 133.2, 129.9, 129.7 (2s), 129.6, 129.1, 129.0, 128.8, 128.4,
128.3, 96.0, 72.0, 70.7, 69.7, 68.7, 67.7, 63.3, 31.3, 19.2, 13.6.
Butyl 2,3,4,6-tetra-O-methyl-r-D-glucopyranoside 8r: 1H NMR
(CDCl3, 500 MHz) δ 5.77 (1H, d, J = 2.0 Hz, H-1), 3.92 (2H, m),
3.83 (1H, m), 3.69 (2H, m), 3.66 (3H, s), 3.62 (2H, m), 3.60 (3H, s),
3.57 (3H, s), 3.53 (2H, m), 1.66 (2H, m), 1.40 (2H, m), 0.94 (3H, t,
J = 7.4 Hz); 13C NMR (CDCl3, 125 MHz) δ 96.3, 83.4, 81.7, 79.6,
71.1, 69.9, 67.8, 60.8, 60.4, 59.2, 58.6, 31.5, 19.8, 13.8.
Butyl 2,3,4,6-tetra-O-acetyl-1-r-D-thioglucopyranoside 9r:
IR (film) (cm-1) 2960, 2873, 1723, 1451, 1265, 1107, 1095, 1069,
1026; 1H NMR (CDCl3, 500 MHz) δ 5.66 (1H, d, J = 5.8 Hz),
5.38 (1H, t, J = 9.7Hz), 5.05 (2H, m), 5.46 (1H, ddd, J = 10.2 Hz,
J = 4.7 Hz, J = 2.2 Hz), 4.33 (1H, dd, J = 12.4 Hz, J = 4.7 Hz),
4.12 (1H, dd, J = 12.4 Hz, J = 2.2 Hz), 2.54 (2H, m), 2.16 (3H, s),
2.09 (3H, s), 2.08 (3H, s), 2.05 (3H, s), 1.58 (2H, m), 1.40 (2H, m),
0.92 (3H, t, J = 7.4 Hz); 13C NMR (CDCl3, 125 MHz) δ 170.6,
169.9 (2s), 169.6, 82.0, 70.8, 70.5, 68.6, 67.5, 62.0, 31.4, 29.8, 21.9,
20.8, 20.70 (2s), 20.6, 13.6; ESI-HRMS calcd for C18H28O9SNa
443.1352, found m/z 443.1360 [M þ Na]þ.
Butyl 2,3,4-tri-O-acetyl-r-D-glucopyranosiduronic acid, methyl
ester 2r: IR (film) (cm-1) 2960, 1754, 1439, 1371, 1219, 1051;
1H NMR (CDCl3, 500 MHz) δ5.55 (1H, t, J = 10.0 Hz), 5.28 (1H,
d, J = 3.6 Hz), 5.21 (1H, t, J = 10.0 Hz), 4.90 (1H, dd, J = 10.0
Hz, J = 3.6 Hz), 4.39 (1H, d, J = 10.0 Hz), 3.80 (3H, s), 3.77 (1H,
m), 3.50 (1H, dt, J = 9.9 Hz, J = 6.5 Hz), 2.09 (3H, s), 2.07 (3H, s),
2.06 (3H, s), 1.60 (2H, m), 1.40 (2H, m), 0.94 (3H, t, J = 7.4 Hz);
13C NMR (CDCl3, 125 MHz) δ 170.7, 170.5, 170.2, 169.1 (each
CdO), 96.1, 70.7, 69.7, 69.6, 69.3, 68.0, 53.5, 31.2, 20.7, 20.6 (2s),
19.1, 13.9; ESI-HRMS calcd for C17H30O10N 408.1870, found
m/z 408.1870 [M þ NH4]þ.
Butyl 2,3,4-tri-O-benzoyl-r-D-glucopyranosiduronic acid, methyl
ester 3r: IR (film) (cm-1) 2958, 1730, 1263, 1107, 1069; 1H NMR
(CDCl3, 500 MHz) δ 7.97 (4H, m), 7.89 (2H, dd, J = 8.1 Hz, J =
0.9 Hz), 7.52 (2H, m), 7.44 (1H, t, J = 7.4 Hz), 7.43 (4H, m), 7.31
(2H, t, J = 7.8 Hz), 6.20 (1H, t, J = 10.0 Hz), 5.64 (1H, t, J = 10.0
Hz), 5.43 (1H, d, J = 3.7 Hz), 5.32 (1H, dd, J = 10.0 Hz, J = 3.7
Hz), 4.62 (1H, d, J = 10.0 Hz), 3.83 (1H, dt, J = 9.9 Hz, J = 6.5
Hz), 3.69 (3H, s), 3.51 (1H, dt, J = 9.9. Hz, J = 6.5 Hz), 1.59 (2H,
m), 1.37 (2H, m), 0.84 (3H, t); 13C NMR (CDCl3, 100 MHz) δ
168.3, 165.7, 165.6, 165.3, 133.4, 133.2, 129.9, 129.8, 129.7, 129.1,
129.0, 128.9, 128.4 (2s), 128.3, 96.3, 71.5, 70.3, 69.8, 69.2, 68.6, 52.9,
31.3, 19.1, 13.6; ESI-HRMS calcd for C32H36O10N 594.2339,
found m/z 594.2326 [M þ NH4]þ.
Butyl 2,3,4,6-tetra-O-benzoyl-1-r-thiobutylglucopyranoside 10r:
IR (film) (cm-1) 2958, 1726, 1267, 1093, 1069, 1027, 708; 1H NMR
(CDCl3, 500 MHz) δ 8.05 (2H, d, J = 7.3 Hz), 7.98 (2H, d, J = 7.3
Hz), 7.95 (2H, d, J = 7.3 Hz), 7.87 (2H, d, J = 7.3 Hz), 7.56 (1H, t,
J =7.3 Hz), 7.51 (2H, t, J = 7.4 Hz), 7.45-7.35 (7H, m), 7.30 (2H,
t, J = 7.8 Hz), 6.07 (1H, t, J = 10.0 Hz), 5.91 (1H, d, J = 5.8 Hz),
5.66 (1H, t, J = 10.0 Hz), 5.50 (1H, dd, J = 10.0 Hz, J = 5.8 Hz),
4.87 (1H, ddd, J = 10.0 Hz, J = 5.6 Hz, J = 2.8 Hz), 4.59 (1H, dd,
J = 12.2 Hz, J = 2.8 Hz), 4.52 (1H, dd, J = 12.2 Hz, J = 5.6 Hz),
2.59 (2H, m), 1.56 (2H, m), 1.30 (2H, m), 0.82 (3H, t, J = 7.4 Hz);
13C NMR (CDCl3, 125 MHz) δ 166.1, 165.6, 165.4, 165.3, 133.4,
133.2, 133.1, 130.0, 129.9, 129.7 (2s), 128.4 (3s), 128.3, 82.3, 71.7,
70.9, 69.6, 68.2, 63.1, 31.4, 29.9, 22.0, 13.5; ESI-HRMS calcd for
C38H36O9SNa 691.1978, found m/z 691.1982 [M þ Na]þ.
Methyl 1-r-thiobutyl-2,3,4-tri-O-acetyl-D-glucopyranosiduronate
4r: IR (film) (cm-1) 2958, 1753, 1438, 1372, 1220, 1042, 899; 1H
NMR (CDCl3, 500 MHz) δ 5.81 (1H, d, J = 5.5 Hz), 5.39 (1H, t,
J = 9.5 Hz), 5.22 (1H, t, J = 9.5Hz), 5.04 (1H, dd, J= 9.5 Hz, J =
5.5 Hz), 4.81 (1H, d, J = 9.5 Hz), 3.80 (3H, s), 2.61 (2H, m), 2.10
(3H, s), 2.08 (3H, s), 2.06 (3H, s), 1.58 (2H, m), 1.41 (2H, m), 0.91
(3H, t, J = 7.4 Hz); 13C NMR (CDCl3, 125 MHz) δ 170.2 (3s),
168.7, 82.3, 70.3, 69.7, 69.5, 68.5, 53.3, 31.4, 30.3, 21.8, 20.7, 20.6,
13.5; ESI-HRMS calcd for C17H30O9NS 424.1641, found m/z
424.1628 [M þ NH4]þ.
Methyl 1-r-thiobutyl-2,3,4-tri-O-benzoyl-D-glucopyranosiduro-
Butyl 2,3,4,6-tetra-O-acetyl-r-D-galactopyranoside 11r: IR
(film) (cm-1) 2961, 2937, 1744, 1369, 12171044, 912; 1H NMR
(CDCl3, 500 MHz) δ 5.46 (1H, d, J = 3.1 Hz), 5.36 (1H, m), 5.10
(2H, m), 4.22 (1H, t, J = 6.6 Hz), 4.11 (1H, dd, J = 9.3 Hz, J =
4.5 Hz), 4.08 (1H, dd J = 9.3 Hz, J = 5.4 Hz), 3.69 (1H, dt, J =
9.7 Hz, J = 6.5 Hz), 3.43 (1H, dt, J = 9.7 Hz, J = 6.5 Hz), 2.14
(3H, s), 2.07 (3H, s), 2.05 (3H, s), 1.99 (3H, s), 1.58 (2H, m), 1.39
(2H, m), 0.93 (3H, t, J = 7.4 Hz); 13C NMR (CDCl3, 125 MHz)
δ 170.4 (2s), 170.2, 170.0, 96.1, 68.4, 68.3, 68.2, 67.7, 66.2, 61.9,
31.3, 20.8, 20.7, 20.6, 19.2, 13.7; ESI-HRMS calcd for C18H32-
O10N 422.2026, found m/z 422.2032 [M þ NH4]þ.
1
nate 5r: IR (film) (cm-1) 2957, 1727, 1259, 1091, 1026, 910; H
NMR (CDCl3, 500 MHz) δ 8.01 (2H, dd, J = 8.0 Hz, J = 1.2
Hz), 7.95 (2H, dd, J = 8.0 Hz, J = 1.2 Hz), 7.91 (2H, dd, J = 8.0
Hz, J = 1.2 Hz), 7.52 (4H, m), 7.39 (2H, t, J = 7.6 Hz), 7.34 (4H,
m), 6.16 (1H, d, J = 5.3 Hz), 6.09 (1H, t, J = 8.9 Hz), 5.78 (1H, t,
J = 8.9 Hz), 5.56 (1H, dd, J = 8.9 Hz, J = 5.3 Hz), 5.16 (1H, d,
J = 8.9 Hz), 3.77 (3H, s), 2.82 (1H, ddd, J = 12.8 Hz, J = 7.9 Hz,
J = 6.5 Hz), 2.76 (1H, ddd, J = 14.9 Hz, J = 7.9 Hz, J = 7.0 Hz),
1.69 (2H, m), 1.46 (2H, m), 0.95 (3H, t, J = 7.4 Hz); 13C NMR
(CDCl3, 125 MHz) δ 168.3, 165.4, 165.3, 165.2, 133.5, 133.4,
130.0, 129.9, 129.8 (3s), 128.9 (2s), 128.8, 128.5, 128.4 (3s), 128.3,
82.0, 70.9, 69.8, 69.5 (2s), 52.8, 31.6, 30.6, 21.9, 13.5; ESI-HRMS
calcd for C32H32O9SNa 615.1665, found m/z 615.1652 [M þ Na]þ.
Butyl 2,3,4-tri-O-acetyl-r-D-galactopyranosiduronic acid, methyl
ester 6r: IR (film) (cm-1) 2958, 1752, 1372, 1224, 1158, 1068, 1030;
1H NMR (CDCl3, 500 MHz) δ 5.77 (1H, dd, J = 3.4 Hz, J = 1.3
Hz), 5.41 (1H, dd, J = 10.9 Hz, J = 3.4 Hz), 5.24 (1H, d, J = 3.6
Hz), 5.16 (1H, dd, J = 10.9 Hz, J = 3.6 Hz), 4.63 (1H, d, J = 1.3
Hz), 3.76 (3H, s, OCH3), 3.74(1H, dt, J =9.9Hz, J= 6.5 Hz), 3.47
(1H,dt,J=9.9Hz,J= 6.7 Hz), 2.10 (3H, s), 2.07 (3H, s), 2.00 (3H,
Butyl 2,3,4,6-tetra-O-benzoyl-r-D-galactopyranoside 12r: IR
(film) (cm-1) 2960, 2873, 1725, 1602, 1267, 1108, 1095, 1069,
1027; 1H NMR (CDCl3, 500 MHz) δ 8.09 (2H, dd, J = 8.3 Hz,
J = 1.2 Hz), 8.02 (2H, dd, J = 8.5 Hz, J = 1.3 Hz), 7.98 (2H, dd,
J=8.5Hz, J=1.3Hz), 7.79(2H, dd, J=8.4Hz, J=1.2Hz), 7.62
(1H, t, J = 7.5 Hz), 7.57-7.36 (9H, m), 7.24 (2H, t, J = 7.8 Hz),
6.04 (1H, d, J = 3.3 Hz), 6.00 (1H, dd, J = 10.6 Hz, J = 3.3 Hz),
5.68 (1H, dd, J = 10.6 Hz, J = 3.6 Hz), 5.41 (1H, d, J = 3.6 Hz),
4.65 (1H, m), 4.60 (1H, dd, J = 11.0, J = 7.1 Hz), 4.40 (1H, dd,
J = 11.0 Hz, J = 5.6 Hz), 3.80 (1H, dt, J = 9.7 Hz, J = 6.5 Hz),
6754 J. Org. Chem. Vol. 75, No. 20, 2010