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1,2,3,4,6-Penta-O-acetyl-a-D-mannopyranoside9 (2b). Isolated
1-O-Methyl-2,3,4,6-tetra-O-acetyl-a-D-glucopyranoside18 (2h).
as white solid following elution of the column with 20% EA–PE; Isolated as white solid following elution of the column with 20%
yield 95%. 1H-NMR (400 MHz, CDCl3) d 6.02 (d, J ¼ 1.8 Hz, 1H), EA–PE; yield 98%. 1H-NMR (400 MHz, CDCl3) d 5.41 (dd, J ¼ 10.0
5.28 (dd, J ¼ 10.0 and 9.6 Hz, 2H), 5.20 (dd, J ¼ 2.3 and 2.0 Hz, and 9.2 Hz, 1H), 5.00 (dd, J ¼ 9.6 and 9.6 Hz, 1H), 4.86 (dd, J ¼
1H), 4.22 (dd, J ¼ 4.9 and 4.9 Hz, 1H), 4.04 (dd, J ¼ 2.4 and 2.4 10.4 and 2.4 Hz, 2H), 4.20 (dd, J ¼ 4 and 4 Hz, 1H), 4.04 (d, J ¼ 12
Hz, 2H), 2.12 (s, 3H), 2.11 (s, 3H), 2.03 (s, 3H), 1.99 (s, 3H), 1.94 Hz, 1H), 3.92 (d, J ¼ 7.6 Hz, 1H), 3.35 (s, 3H), 2.03 (s, 3H), 2.01 (s,
(s, 3H); 13C-NMR (100 MHz, CDCl3) d 170.7, 170.0, 169.8, 169.6, 3H), 1.96 (s, 3H), 1.94 (s, 3H); 13C-NMR (100 MHz, CDCl3) d
168.1, 90.6, 70.6, 68.8, 68.3, 65.5, 62.1, 20.9, 20.8, 20.73, 20.67, 170.7, 170.1, 170.0, 169.6, 96.7, 70.7, 70.0, 68.5, 67.1, 61.9, 55.4,
20.65.
1,2,3,4,6-Penta-O-acetyl-D-galactopyranoside9 (2c). Isolated
20.71, 20.66, 20.60.
Hexa-O-acetyl-myo-inositol36 (2i). Isolated as white solid
as thick yellow oil following elution of the column with 30% following elution of the column with 20% EA–PE; yield 95%. 1H-
EA–PE; yield 91%. 1H-NMR (400 MHz, CDCl3) d 6.38 (d, J ¼ NMR (400 MHz, CDCl3) d 5.59 (dd, J ¼ 2.4 and 2.0 Hz, 1H), 5.49
2.3 Hz, 1H, a-anomer), 5.71 (d, J ¼ 8.3 Hz, 0.23H, b-anomer), (dd, J ¼ 8.0 and 8.0 Hz, 2H), 5.17 (dd, J ¼ 8.0 and 8.0 Hz, 1H),
5.43 (d, J ¼ 4.3 Hz, 1H), 5.34–5.33 (m, 3H), 5.11–5.07 (m, 1H), 5.08 (dd, J ¼ 2.0 and 2.0 Hz, 2H), 2.20 (s, 3H), 2.03–1.99 (5 s,
4.37–4.34 (m, 1H), 4.15–4.06 (m, 3H), 2.17–2.00 (m, 27H); 15H); 13C-NMR (100 MHz, CDCl3) d 169.8, 169.7, 169.5, 71.0,
13C-NMR (100 MHz, CDCl3) d 170.4, 170.2, 170.1, 169.9, 168.9, 69.4, 68.5, 68.2, 20.8, 20.6, 20.5.
99.0, 92.1, 89.6, 71.6, 70.8, 69.2, 68.7, 67.8, 67.4, 67.3, 66.4, 61.2,
61.0, 20.9, 20.64, 20.62, 20.59, 20.52.
Hexa-O-acetyl-D-mannitol22 (2j). Isolated as white solid
following elution of the column with 20% EA–PE; yield 99%. 1H-
1,3,4,6-Tetra-O-acetyl-2-N-acetyl-a-D-glucosamine15 (2d). Iso- NMR (400 MHz, CDCl3) d 5.44 (d, J ¼ 6.6 Hz, 2H), 5.08–5.05 (m,
lated as white solid following elution of the column with 50% 2H), 4.21 (dd, J ¼ 2.1 and 2.1 Hz, 2H), 4.06 (dd, J ¼ 4.1 and 4.1
EA–PE; yield 96%. 1H-NMR (400 MHz, CDCl3) d 6.17 (d, J ¼ 3.6 Hz, 2H), 2.08–2.04 (s, 18H); 13C-NMR (100 MHz, CDCl3) d 170.6,
Hz, 1H), 5.59 (d, J ¼ 8.8 Hz, 1H), 5.23 (dd, J ¼ 4.8 and 2.4 Hz, 169.9, 169.7, 67.8, 67.4, 61.8, 20.9, 20.7, 20.6.
2H), 4.50 (dd, J ¼ 3.6 and 3.2 Hz, 1H), 4.31 (dd, J ¼ 4.0 and 4.0
D-Maltose octa-O-acetate18 (2k). Isolated as white solid
Hz, 1H), 4.07 (dd, J ¼ 2.4 and 2.4 Hz, 1H), 4.00 (bs, 1H), 2.20 (s, following elution of the column with 30% EA–PE; yield 99%. 1H-
3H), 2.09 (s, 3H), 2.06 (s, 3H), 2.05 (s, 3H), 1.95 (s, 3H); 13C-NMR NMR (400 MHz, CDCl3) d 6.22 (d, J ¼ 3.7 Hz, 0.73H, a-anomer),
(100 MHz, CDCl3) d 171.9, 170.7, 170.0, 169.1, 168.7, 90.6, 70.6, 5.72 (d, J ¼ 8.1 Hz, 1H, b-anomer), 5.41 (dd, J ¼ 8.4 and 3.9 Hz,
69.7, 67.5, 61.5, 51.0, 23.0, 20.9, 20.7, 20.6.
1H), 5.38–5.25 (m, 5H), 5.06–4.98 (m, 2H), 4.96–4.93 (m, 2H),
1,3,4,6-Tetra-O-acetyl-2-deoxy-2-phthalimido-b-D-glucopyr- 4.87–4.82 (m, 2H), 4.45–4.41 (m, 2H), 4.25–4.20 (m, 4H), 4.08–
anoside35 (2e). Isolated as white crystals following elution of the 3.99 (m, 4H), 3.94–3.91 (m, 2H), 3.84–3.80 (m, 1H), 2.20–1.97
column with 20% EA–PE; yield 80%. 1H-NMR (400 MHz, CDCl3) (m, 44H); 13C-NMR (100 MHz, CDCl3) d 170.6, 170.5, 170.4,
d 7.88 (dd, J ¼ 3.0 and 3.0 Hz, 2H), 7.77 (dd, J ¼ 3.0 and 3.0 Hz, 170.1, 169.9, 169.6, 169.5, 168.8, 95.7, 91.2, 88.8, 76.7, 75.2, 72.9,
2H), 6.53 (d, J ¼ 8.9 Hz, 1H), 5.89 (dd, J ¼ 9.1 and 9.1 Hz, 1H), 72.4, 70.9, 69.2, 68.6, 62.5, 61.4, 21.0, 20.94, 20.88, 20.82, 20.7,
5.23 (dd, J ¼ 9.2 and 9.2 Hz, 1H), 4.48 (dd, J ¼ 8.9 and 8.9 Hz, 20.6, 20.5, 20.4.
1H), 4.38 (dd, J ¼ 4.4 and 4.4 Hz, 1H), 4.16 (dd, J ¼ 2.1 and 2.1
Sucrose octa-O-acetate37(2l). Isolated as thick oil following
Hz), 4.06–4.02 (m, 1H), 2.13 (s, 3H), 2.05 (s, 3H), 2.01 (s, 3H), elution of the column with 20% EA–PE; 97%. 1H-NMR (400
1.88 (s, 3H); 13C-NMR (100 MHz, CDCl3) d 170.7, 170.1, 169.5, MHz, CDCl3) d 5.69 (d, J ¼ 3.7 Hz, 1H), 5.47–5.42 (m, 2H), 5.37 (t,
168.7, 168.2, 167.4, 134.5, 131.2, 123.8, 89.7, 72.6, 70.5, 68.3, J ¼ 5.9 and 5.9 Hz, 2H), 5.07 (dd, J ¼ 9.7 and 8.7 Hz, 1H), 4.87
61.5, 53.5, 20.8, 20.7, 20.6, 20.4.
(dd, J ¼ 3.7 and 2.4 Hz, 1H), 4.37–4.13 (m, 8H), 2.18 (s, 3H),
1,3,4,6-Tetra-O-acetyl-2-deoxy-2-azido-D-glucopyranoside9 (2f). 2.12–2.10 (s, 15H), 2.05 (s, 3H), 2.02 (s, 3H); 13C-NMR (100 MHz,
Isolated as white solid following elution of the column with 20% CDCl3) d 170.8, 170.5, 170.2, 170.1, 170.0, 169.9, 169.7, 169.6,
EA–PE; yield 95%. 1H-NMR (400 MHz, CDCl3) d 6.30 (d, J ¼ 4.0 104.0, 89.9, 79.1, 75.6, 74.9, 70.2, 69.6, 68.5, 68.1, 63.6, 62.8,
Hz, 0.22H, a-anomer), 5.55 (d, J ¼ 8.8 Hz, 1H, b-anomer), 5.11– 61.7, 20.74, 20.71, 20.67, 20.63, 20.60, 20.58.
5.02 (m, 2H), 4.33–4.28 (m, 1H), 4.10–4.07 (m, 1H), 3.82–3.78
Per-O-acetylated b-cyclodextrin9 (2m). Isolated as white solid
(m, 1H), 3.69–3.65 (m, 1H), 2.19–2.03 (m, 12H); 13C-NMR (100 following elution of the column with 20% EA–PE; yield 98%. 1H-
MHz, CDCl3) d 170.5, 169.8, 169.6, 168.5, 92.5, 89.9, 72.7, 72.6, NMR (400 MHz, CDCl3) d 5.30 (dd, J ¼ 8.2 and 8.2 Hz, 7H), 5.09
70.7, 69.7, 67.8, 67.7, 62.5, 61.4, 60.3, 20.9, 20.7, 20.6, 20.5.
(dd, J ¼ 3.9 and 3.9 Hz, 7H), 4.80 (dd, J ¼ 3.9 and 3.9 Hz, 7H),
1,2,3,4-Tetra-O-acetyl-D-xylopyranoside18 (2g). Isolated as 4.56 (d, J ¼ 11.2 Hz, 7H), 4.27 (dd, J ¼ 4.2 and 4.2 Hz, 7H), 4.14
colourless oil following elution of the column with 20% EA–PE; (m, 7H), 3.70 (dd, J ¼ 8.2 and 8.1 Hz, 7H), 2.13–2.06 (3s, 63H);
yield 90%. 1H-NMR (400 MHz, CDCl3) d 6.26 (d, J ¼ 3.6 Hz, 1H, 13C-NMR (100 MHz, CDCl3) d 170.7, 170.4, 169.5, 96.7, 70.8,
a-anomer), 5.72 (d, J ¼ 6.9 Hz, 0.23H, b-anomer), 5.47 (t, J ¼ 10.0 70.4, 69.6, 62.5, 20.8.
Hz, 1H), 5.38–5.21 (m, 1H), 5.05–5.01 (m, 3H), 4.65 (d, J ¼ 8 Hz,
0.49H), 4.27–4.21 (m, 1H), 3.95–3.92 (m, 1H), 3.74–3.69 (m, 1H),
General procedure for one-pot per-O-acetylation–
thioglycosylation of sugars
3.56–3.51 (m, 0.24H), 2.18–2.03 (m, 24H); 13C-NMR (100 MHz,
CDCl3) d 170.5, 170.1, 169.8, 169.7, 169.6, 169.0, 168.2, 168.1,
Per-O-acetylation of sugar was carried out as described above.
When reaction was completed according to TLC, p-thiocresol
(2 equiv.) and BF3–Et2O (2 equiv.) were sequentially added to the
98.7, 92.7, 91.9, 89.2, 79.8, 79.4, 74.2, 69.3, 68.6, 62.7, 62.3, 61.6,
60.6, 21.0, 20.8, 20.7, 20.64, 20.57, 20.53, 20.47, 20.40.
29672 | RSC Adv., 2015, 5, 29669–29674
This journal is © The Royal Society of Chemistry 2015