Organic & Biomolecular Chemistry
Paper
1H NMR (400 MHz, CDCl3): δ 7.38–7.20 (m, 4H, PMB), Methyl 2-O-dodecyloxycarbonylmethyl-3,4-di-O-(4-
6.99–6.82 (m, 4H, PMB), 4.79–4.46 (m, 5H, 2 × OCH2, H-1), methoxybenzyl)-6-O-phthalimido-α-D-glucopyranoside (16)
4.40 (d, J = 17.4 Hz, 1H, OCH), 4.32 (d, J = 17.4 Hz, 1H, OCH),
The phthalimido group was introduced at the 6-position of
4.02–3.75 (m, 8H, 2 × OCH3, H-6), 3.71 (t, J = 8.9 Hz, 1H, H-3),
compound 15 (55 mg, 0.083 mmol) using the Mitsunobu reac-
3.61–3.43 (m, 3H, H-2,4,5), 3.30 (s, 3H, OCH3), 0.91 (s, 9H,
tion according to the general procedure. Purification by
column chromatography over silica gel (petroleum ether/
EtOAc: 3/1) afforded the desired compound (66 mg, 98%) as a
tBu), 0.16–0.02 (m, 6H, Si(CH3)2); 13C NMR (100 MHz, CDCl3):
δ 172.1 (CvO), 159.9, 159.7 (Cq); 130.2, 130.0 (CH); 129.5,
128.6 (Cq); 114.2, 114.1 (CH); 96.8 (C-1), 82.0, 78.5, 77.6 (CH);
74.8, 72.4 (CH2); 71.5 (CH), 70.5, 61.9 (CH2); 55.4, 55.1 (OCH3);
26.0 (CH3, tBu), 18.4 (Cq, tBu), −5.0, −5.2 (CH3, Si(CH3)2);
HRMS (ESI) m/z 629.2759, Calcd for C31H46NaO10Si [M + Na]+
629.2758.
colourless paste: Rf = 0.77 (petroleum ether–EtOAc 1/1); [α]D
+
65.7 (c 0.1, CHCl3); 1H NMR (400 MHz, CDCl3): δ 7.88–7.72 (m,
4H, Phth), 7.36–7.26 (m, 4H, PMB), 6.91–6.82 (m, 4H, PMB),
4.98 (d, J = 10.1 Hz, 1H, OCH), 4.82 (d, J = 10.1 Hz, 1H, OCH),
4.75–4.33 (m, 7H, 2 × OCH2, H-1,6), 4.15 (t, J = 6.9 Hz, 2H,
OCH2), 3.91–3.72 (m, 9H, 2 × OCH3, H-3,4,5), 3.58 (dd, J = 9.1,
3.4 Hz, 1H, H-2), 3.35 (s, 3H, OCH3), 1.70–1.57 (m, 2H, CH2),
1.43–1.19 (m, 18H, 9 × CH2), 0.88 (t, J = 6.8 Hz, 3H, CH3);
13C NMR (100 MHz, CDCl3): δ 170.3, 163.3 (CvO); 159.5, 159.3
(Cq); 134.6 (CH), 130.6, 130.2 (Cq); 130.1, 129.9 (CH); 129.0
(Cq), 123.6 (CH), 113.93, 113.88 (CH); 98.2 (C-1), 83.4, 79.1
(CH); 76.4 (CH2), 76.0 (CH), 74.9, 73.1, 70.9 (CH2); 69.1 (CH),
65.1 (CH2), 55.6, 55.3 (OCH3); 32.0, 29.8, 29.7, 29.6, 29.5, 29.4,
28.7, 26.0, 22.8 (CH2); 14.3 (CH3); HRMS (ESI) m/z 844.3678,
Calcd for C45H59KNO12 [M + K]+ 844.3674.
Methyl 2-O-dodecyloxycarbonylmethyl-3,4-di-O-(4-
methoxybenzyl)-6-O-tert-butyldimethylsilyl-α-D-
glucopyranoside (14)
Esterification of compound 13 (148 mg, 0.24 mmol) with
1-dodecanol according to the general procedure and purifi-
cation by column chromatography over silica gel (petroleum
ether/EtOAc: 5/1) afforded compound 14 (144 mg, 76%) as a
white paste: Rf = 0.63 (petroleum ether–EtOAc 4/1); [α]D + 23.0
1
(c 0.1, CHCl3); H NMR (400 MHz, CDCl3): δ 7.50–7.19 (m, 4H,
PMB), 7.05–6.80 (m, 4H, PMB), 5.00–4.32 (m, 7H, 3 × OCH2,
H-1), 4.10 (t, J = 6.7 Hz, 2H, OCH2), 4.04–3.68 (m, 9H, 2 ×
OCH3, H-3,6), 3.64–3.44 (m, 3H, H-2,4,5), 3.26 (s, 3H, OCH3),
1.70–1.54 (m, 2H, CH2), 1.52–1.17 (m, 18H, 9 × CH2), 1.02–0.82
(m, 12H, tBu, CH3), 0.16–0.02 (m, 6H, Si(CH3)2); 13C NMR
(100 MHz, CDCl3): δ 170.4 (CvO), 159.4, 159.3, 130.7, 130.3
(Cq); 129.8, 113.8 (CH); 97.7 (C-1), 83.6, 79.7, 76.8 (CH); 74.7,
73.0 (CH2); 71.3 (CH), 70.9, 65.0, 62.3 (CH2); 55.3, 54.9 (OCH3);
32.0, 29.7, 29.6, 29.4, 29.3, 28.7 (CH2); 26.0 (CH3, tBu), 25.9,
22.8 (CH2); 18.4 (Cq, tBu), 14.2 (CH3), −5.1, −5.3 (CH3,
Si(CH3)2); HRMS (ESI) m/z 797.4639, Calcd for C43H70NaO10Si
[M + Na]+ 797.4636.
Methyl 6-O-amino-2-O-dodecyloxycarbonylmethyl-3,4-di-O-(4-
methoxybenzyl)-α-D-glucopyranoside (17)
Hydrazinolysis of compound 16 (58 mg, 0.071 mmol) according
to the general procedure and purification by column chromato-
graphy over silica gel (petroleum ether/EtOAc: 1/1) afforded
compound 17 (35 mg, 73%) as a yellowish paste: Rf = 0.39
(petroleum ether–EtOAc 1/1); [α]D + 45.3 (c 0.1, CHCl3); 1H NMR
(400 MHz, CDCl3): δ 7.34–7.24 (m, 4H, PMB), 6.93–6.84 (m, 4H,
PMB), 4.93–4.34 (m, 7H, 3 × OCH2, H-1), 4.13 (t, J = 6.8 Hz, 2H,
OCH2), 3.91–3.74 (m, 9H, 2 × OCH3, H-3,6), 3.72–3.65 (m, 1H,
H-5), 3.56–3.45 (m, 2H, H-2,4), 3.30 (s, 3H, OCH3), 1.69–1.57 (m,
2H, CH2), 1.39–1.17 (m, 18H, 9 × CH2), 0.88 (t, J = 6.8 Hz, 3H,
CH3); 13C NMR (100 MHz, CDCl3): δ 170.4 (CvO), 159.5, 159.4,
130.5, 130.2 (Cq); 130.1, 129.9, 114.0, 113.9 (CH); 98.1 (C-1),
83.5, 79.4, 76.7 (CH); 74.8, 74.3, 73.1, 70.9 (CH2); 69.4 (CH), 65.0
(CH2), 55.4, 55.3 (OCH3); 32.0, 29.8, 29.7, 29.6, 29.5, 29.4, 28.7,
26.0, 22.8 (CH2); 14.3 (CH3); HRMS (ESI) m/z 698.3884, Calcd
for C37H57NaNO10 [M + Na]+ 698.3880.
Methyl 2-O-dodecyloxycarbonylmethyl-3,4-di-O-(4-
methoxybenzyl)-α-D-glucopyranoside (15)
Desilylation of compound 14 (74 mg, 0.096 mmol) according
to the general procedure and purification by column chromato-
graphy over silica gel (petroleum ether/EtOAc: 1/1) afforded
compound 15 (45 mg, 71%) as a colourless paste: Rf = 0.10
(petroleum ether–EtOAc 3/1); [α]D + 56.7 (c 0.1, CHCl3); 1H
NMR (400 MHz, CDCl3): δ 7.40–7.22 (m, 4H, PMB), 7.00–6.81
Methyl 3,4-di-O-(4-methoxybenzyl)-2-O-palmitoyl-6-O-tert-
butyldimethylsilyl-α-D-glucopyranoside (18)
(m, 4H, PMB), 4.91–4.35 (m, 7H, 3 × OCH2, H-1), 4.10 (t, J = 6.8 Esterification of compound 4 (0.62 g, 1.13 mmol) with palmitic
Hz, 2H, OCH2), 3.91–3.73 (m, 7H, 2 × OCH3, H-3′), 3.73 (dd, J = acid according to the general procedure and purification by
11.9, 2.8 Hz, 1H, H-6a), 3.65 (dd, J = 11.9, 3.2 Hz, 1H, H-6b), column chromatography over silica gel (petroleum ether/
3.57–3.43 (m, 3H, H-2,4,5), 3.26 (s, 3H, OCH3), 1.79 (s, 1H, EtOAc: 8/1) afforded compound 18 (0.88 g, 99%) as a colour-
OH), 1.65–1.55 (m, 2H, CH2), 1.40–1.18 (m, 18H, 9 × CH2), 0.85 less paste: Rf = 0.78 (petroleum ether–EtOAc 3/1); [α]D + 26.0
1
(t, J = 6.8 Hz, 3H, CH3); 13C NMR (100 MHz, CDCl3): δ 170.4 (c 0.1, CHCl3); H NMR (400 MHz, CDCl3): δ 7.25–7.14 (m, 4H,
(CvO), 159.5, 159.4, 130.4, 130.1 (Cq); 130.0, 129.8, 113.9 PMB), 6.94–6.81 (m, 4H, PMB), 5.53 (t, J = 9.6 Hz, 1H, H-3),
(CH); 98.0 (C-1), 83.3, 79.6, 76.4 (CH); 74.7, 73.0, 70.8 (CH2); 4.61–4.47 (m, 5H, 2 × OCH2, H-1), 3.90–3.74 (m, 8H, 2 × OCH3,
70.5 (CH), 65.0, 61.9 (CH2); 55.3, 55.2 (OCH3); 32.0, 29.7, 29.6, H-6), 3.68–3.62 (m, 1H, H-5), 3.52 (t, J = 9.6 Hz, 1H, H-4),
29.4, 29.3, 28.7, 25.9, 22.8 (CH2); 14.2 (CH3); HRMS (ESI) m/z 3.43–3.36 (m, 1H, H-2), 3.33 (s, 3H, OCH3), 2.26–2.18 (m, 2H,
683.3775, Calcd for C37H56NaO10 [M + Na]+ 683.3771.
CH2), 1.68–1.55 (m, 2H, CH2), 1.50–1.16 (m, 24H, 12 × CH2),
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