4.2.5.6 (2S,3R,4S,5S,6R)-6-(Acetoxymethyl)-3-dodecanamidotetrahydro-2H-pyran-2,4,5-triyl triacetate (8f)
The title compound was synthesized from acetoxy glucosamine 7 (1.00 g, 2.88 mmol) and dodecanoic acid (0.69 g, 3.45 mmol)
1
following GSP-1 to yield a white solid (1.16 g, 76%). M.p. 117–118 ºC; Optical rotation: [α]25589 +18.0 (MeOH); H NMR (300
MHz, DMSO-d6): δ 0.85 (t, J = 6.9 Hz, 3H, CH3), 1.11–1.34 (m, 16H, 8 x CH2), 1.34–1.47 (m, 2H, CH2), 1.75–1.87 (m, 2H, CH2),
1.90 (s, 3H, CH3), 1.97 (s, 3H, CH3), 2.00 (s, 3H, CH3), 2.02 (s, 3H, CH3), 3.91–3.94 (m, 1H, CH), 3.95–4.02 (m, 2H, CH2), 4.18
(dd, J = 4.6, 4.6 Hz, 1H, CH), 4.88 (t, J = 9.3 Hz, 1H, CH), 5.19 (t, J = 9.9 Hz, 1H, CH), 5.71 (d, J = 8.8 Hz, 1H, CH), 7.91 (d, J =
9.0 Hz, 1H, NH); 13C NMR (75 MHz, DMSO-d6): δ 14.4 (CH3), 20.8 (CH3), 20.9 (CH3), 21.0 (2 x CH3), 22.5 (CH2), 25.7 (CH2),
28.8 (CH2), 29.1 (CH2), 29.2 (CH2), 29.3 (CH2), 29.5 (2x CH2), 31.7 (CH2), 35.9 (CH2), 52.2 (CH), 61.9 (CH2), 68.6 (CH), 72.0
(CH), 72.6 (CH), 92.2 (CH), 169.2 (CO), 169.7 (CO), 169.9 (CO), 170.5 (CO), 172.9 (CO); IR (neat): νmax 903, 1035, 1212, 1369,
1525, 1660, 1738, 2848, 2917, 3338 cm-1; HRMS (+ESI): Found m/z 552.2775 [M + Na]+, C26H43NO10Na requires 552.2779.
4.2.5.7. (2S,3R,4S,5S,6R)-3-(2-(1H-Indol-3-yl)acetamido)-6-(acetoxymethyl)tetrahydro-2H-pyran-2,4,5-triyl triacetate (8g)
The title compound was synthesized from acetoxy glucosamine 7 (0.69 g, 1.98 mmol) and 3-indole acetic acid (0.43 g, 2.44 mmol)
1
following GSP-1 to yield a white solid (0.57 g, 57%). M.p. 196 °C; Optical rotation: [α]25589 +19.2 (MeOH); H NMR (300 MHz,
DMSO-d6): δ 1.72 (s, 3H, CH3), 1.82 (s, 3H, CH3), 1.96 (s, 3H, CH3), 1.99 (s, 3H, CH3), 3.45 (s, 2H, CH2), 3.94–4.03 (m, 3H, CH,
CH2), 4.86 (t, J = 9.6 Hz, 1H, CH), 5.20 (dd, J = 10.5, 9.4 Hz, 1H, CH), 5.72 (d, J = 8.9 Hz, 1H, CH), 6.91–6.96 (m, 1H, ArH),
7.03–7.08 (m, 1H, ArH), 7.12 (d, J = 2.3 Hz, 1H, ArH), 7.32 (d, J = 8.0 Hz, 1H, ArH), 7.46 (d, J = 7.9 Hz, 1H, ArH), 8.02 (d, J =
9.3 Hz, 1H, NH), 10.88 (s, 1H, indole NH); 13C NMR (75 MHz, DMSO-d6): δ 20.1 (CH3), 20.2 (CH3), 20.4 (CH3), 20.5 (CH3), 32.9
(CH2), 51.7 (CH), 61.5 (CH2), 68.2 (CH), 71.5 (CH), 72.0 (CH), 91.7 (CH), 108.4 (ArC), 111.3 (ArCH), 118.3 (ArCH), 118.4
(ArCH), 120.9 (ArCH), 123.8 (ArCH), 127.0 (ArC), 136.1 (ArC), 168.8 (CO), 169.2 (CO), 169.5 (CO), 170.0 (CO), 171.0 (CO); IR
(neat): vmax 677, 738, 791, 838, 923, 1037, 1211, 1369, 1425, 1523, 1666, 1749, 3322, 3420 cm-1; UV (MeOH): λmax 335 nm (ε 2
900 M-1 cm-1), 272 (12 100), 221 (48 200); HRMS (+ESI): Found m/z 527.1635 [M + Na]+, C24H28N2O10Na requires 527.1636.
4.2.5.8. (2S,3R,4S,5S,6R)-3-(3-(1H-Indol-3-yl)propanamido)-6-(acetoxymethyl)tetrahydro-2H-pyran-2,4,5-triyl triacetate (8h)
The title compound was synthesized from acetoxy glucosamine 7 (0.70 g, 2.02 mmol) and 3-indole propionic acid (0.47 g, 2.46
mmol) following GSP-1 to yield a pale brown sticky solid (0.27 g, 26%). M.p. 126 °C; Optical rotation: [α]25589 +20.3 (MeOH); 1H
NMR (300 MHz, MeOD-d4): δ 1.85 (s, 3H, CH3), 1.92 (s, 3H, CH3), 2.00 (s, 3H, CH3), 2.04 (s, 3H, CH3), 2.54 (d, J = 7.4 Hz, 2H,
CH2), 3.01 (d, J = 7.3 Hz, 2H, CH2), 3.86–3.92 (m, 1H, CH), 4.03–4.11 (m, 2H, CH2), 4.27 (dd, J = 12.3, 4.5 Hz, 1H, CH), 5.00 (t, J
= 10.0 Hz, 1H, CH), 5.27 (dd, J = 10.5, 9.3 Hz, 1H, CH), 5.75 (d, J = 8.9 Hz, 1H, CH), 6.96–7.10 (m, 3H, 3 x ArH), 7.29–7.32 (m,
1H, ArH), 7.51–7.54 (m, 1H, ArH); 13C NMR (75 MHz, MeOD-d4): δ 20.4 (CH3), 20.5 (CH3), 20.5 (CH3), 20.6 (CH3), 22.3 (CH2),
37.8 (CH2), 54.1 (CH), 62.9 (CH2), 69.7 (CH), 73.7 (CH), 93.3 (CH), 112.2 (ArC), 114.8 (ArC), 119.2 (ArCH), 119.6 (ArCH),
122.4 (ArCH), 122.8 (ArCH), 128.5 (ArC), 138.1 (ArC), 170.7 (CO), 171.2 (CO), 171.8 (CO), 172.3 (CO), 176.1 (CO); IR (neat):
vmax 747, 845, 909, 1030, 1213, 1367, 1421, 1519, 1662, 1738, 2117, 2353, 2961, 3399 cm-1; UV (MeOH): λmax 280 nm (ε 4 400 M-1
cm-1), 219 (25 200); HRMS (+ESI): Found m/z 541.1792 [M + Na]+, C25H30N2O10Na requires 541.1793.
4.2.5.9. (2S,3R,4S,5S,6R)-6-(Acetoxymethyl)-3-(2-(4-fluorophenyl)acetamido)tetrahydro-2H-pyran-2,4,5-triyl triacetate (8i)
The title compound was synthesized from acetoxy glucosamine 7 (0.69 g, 1.99 mmol) and 4-fluorophenyl acetic acid (0.37 g, 2.41
1
mmol) following GSP-1 to yield a white solid (0.73 g, 75%). M.p. 198 °C; Optical rotation: [α]25589 +10.2 (MeOH); H NMR (300
MHz, DMSO-d6): δ 1.76 (s, 3H, CH3), 1.92 (s, 3H, CH3), 1.96 (s, 3H, CH3), 2.00 (s, 3H, CH3), 3.34 (s, 2H, CH2), 3.90–4.05 (m, 3H,
CH, CH2), 4.18 (dd, J = 12.3, 4.4 Hz, 1H, CH), 4.87 (t, J = 9.8 Hz, 1H, CH), 5.18 (dd, J = 10.6, 9.4 Hz, 1H, CH), 5.72 (d, J = 8.9
Hz, 1H, CH), 7.08–7.14 (m, 2H, 2 x ArH), 7.20–7.24 (m, 2H, 2 x ArH), 8.23 (d, J = 9.2 Hz, 1H, NH); 13C NMR (75 MHz, DMSO-
d6): δ 20.1 (CH3), 20.3 (CH3), 20.4 (CH3), 20.5 (CH3), 41.6 (CH2), 51.8 (CH), 61.5 (CH2), 68.1 (CH), 71.5 (CH), 72.0 (CH), 91.6
(CH), 114.8 (ArCH), 115.1 (ArCH), 130.5 (ArCH), 130.6 (ArCH), 132.3 (ArC), 162.6 (ArC), 168.7 (CO), 169.2 (CO), 169.4 (CO),
170.0 (CO), 170.4 (CO); IR (neat): vmax 825, 909, 1031, 1210, 1374, 1444, 1523, 1655, 1744, 2113, 2299, 2942, 3343 cm-1; HRMS
(+ESI): Found m/z 506.1430 [M + Na]+, C22H26FNO10Na requires 506.1433.
4.2.5.10. (2S,3R,4S,5S,6R)-6-(Acetoxymethyl)-3-(2-(4-chlorophenyl)acetamido)tetrahydro-2H-pyran-2,4,5-triyl triacetate (8j)
The title compound was synthesized from acetoxy glucosamine 7 (0.70 g, 2.02 mmol) and 4-chlorophenyl acetic acid (0.41 g, 2.41
1
mmol) following GSP-1 to yield a white solid (0.75 g, 74%). M.p. 196 °C; Optical rotation: [α]25589 +20.2 (MeOH); H NMR (300
MHz, DMSO-d6): δ 1.77 (s, 3H, CH3), 1.93 (s, 3H, CH3), 1.97 (s, 3H, CH3), 2.01 (s, 3H, CH3), 3.36 (s, 2H, CH2), 3.91–4.05 (m, 3H,
CH, CH2), 4.18 (dd, J = 12.6, 4.5 Hz, 1H, CH), 4.87 (t, J = 9.6 Hz, 1H, CH), 5.19 (t, J = 9.6 Hz, 1H, CH), 5.72 (d, J = 8.7 Hz, 1H,
CH), 7.22 (d, J = 8.4 Hz, 2H, 2 x ArH), 7.36 (d, J = 8.7 Hz, 2H, 2 x ArH), 8.26 (d, J = 9.0 Hz, 1H, NH); 13C NMR (75 MHz,
DMSO-d6): δ 20.1 (CH3), 20.3 (CH3), 20.3 (CH3), 20.4 (CH3), 41.7 (CH2), 51.8 (CH), 61.4 (CH2), 68.0 (CH), 71.5 (CH), 71.9 (CH),
91.6 (CH), 128.1 (2 x ArCH), 130.6 (2 x ArCH), 131.2 (ArC), 135.1 (ArC), 168.7 (CO), 169.2 (CO), 169.4 (CO), 170.0 (CO), 170.1
(CO); IR (neat): vmax 756, 806, 903, 984, 1037, 1218, 1371, 1419, 1524, 1659, 1744, 2110, 2967, 3338 cm-1; UV (MeOH): λmax 221
nm (ε 11 600 M-1 cm-1); HRMS (+ESI): Found m/z 522.1134 [M + Na]+, C22H26ClNO10Na requires 522.1137.
4.2.5.11. (2S,3R,4S,5S,6R)-6-(Acetoxymethyl)-3-(2-(4-bromophenyl)acetamido)tetrahydro-2H-pyran-2,4,5-triyl triacetate (8k)
The title compound was synthesized from acetoxy glucosamine 7 (0.70 g, 2.00 mmol) and 4-bromophenyl acetic acid (0.52 g, 2.41
1
mmol) following GSP-1 to yield a white solid (0.85 g, 78%). M.p. 209 °C; Optical rotation: [α]25 +9.7 (MeOH); H NMR (300
589
Corresponding author. Tel.: +61 2 9385 4698; fax: +61 2 9385 6141.