Organic & Biomolecular Chemistry
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(s, 3H, CH3 PivOAc), 2.04–1.98 (m, 3H, COCH3), 1.88 (dd, J = 14.7, 127.1, 101.5, 97.0, 82.2, 81.2, 79.5, 78.5, 75.3, 75.2, 74.8, 73.6,
7.7 Hz, 2H, CH2 PivOAc), 1.75–1.61 (m, 1H, CH(CH3)2), 72.8, 68.8, 62.9, 62.9, 52.7, 37.8, 34.0, 29.9, 20.8, 20.1, 18.4,
1.23–1.14 (m, 6H, 2 × CH3 PivOAc), 0.94–0.86 (m, 12H, C(CH3)2 −2.1, −3.1. HRMS: m/z: calcd for C49H65N3O14SiNa: 970.4134;
and CH(CH3)2), 0.18 (s, 3H, SiCH3), 0.16 (s, 3H, SiCH3). 13C found: 970.4137 [M + Na]+.
NMR (126 MHz, CDCl3) δ 128.2, 127.9, 128.3, 127.7, 127.2,
127.1, 125.1, 120.5, 120.0, 99.9, 96.7, 80.6, 79.4, 76.8, 75.0,
74.7, 73.7, 72.8, 72.5, 72.3, 70.5, 68.5, 62.6, 62.6, 61.2, 46.6,
53.2, 52.7, 38.2, 33.9, 29.7, 25.3, 24.9, 20.8, 20.9, 20.0, 19.9,
Dimethylthexylsilyl O-(methyl-2-O-(4-acetoxy-
2,2-dimethylbutanoate)-3,4-O-benzyl-β-D-glucopyranosyluronate)-
(1→4)-O-2-deoxy-2-azido-3-O-benzyl-6-O-acetyl-
β-D-glucopyranoside (26)
18.4, −3.2. HRMS: m/z: calcd for C60H75N3O17SiNa: 1160.4763;
found: 1160.4770 [M + Na]+.
Compound 26 (95 mg, 71%) was prepared according to the
general procedure from compound 25 (109 mg, 0.16 mmol)
and compound 17 (63 mg, 0.13 mmol) catalyzed by TfOH (1.4
µL, 0.01 mmol). 1H NMR (500 MHz, CDCl3) δ 7.34–6.96 (m,
15H, CH aromatic), 4.98–4.89 (t, J = 9.3 Hz, 1H, H-2′), 4.82 (d,
Dimethylthexylsilyl O-(methyl-2-O-acetyl-3,4-O-benzyl-
β-D-glucopyranosyluronate)-(1→4)-O-2-deoxy-2-azido-
3-O-benzyl-6-O-acetyl-β-D-glucopyranoside (22)
Compound 22 (16 mg, 22%) was prepared according to the J = 10.8 Hz, 1H, CHHBn), 4.64 (d, J = 11.4 Hz, 1H, CHHBn),
general glycosylation procedure from compounds 21 (55 mg, 4.59–4.40 (m, 5H, CH2 Bn, H-1′), 4.35 (d, J = 7.7 Hz, 1H, H-1),
0.10 mmol) and 17 (38 mg, 0.13 mmol) catalyzed by TfOH 4.17 (dd, J = 11.7, 1.8 Hz, 1H, H-6a), 4.03 (dd, J = 11.8, 5.9 Hz,
(1.0 µL, 0.01 mmol). 1H NMR (500 MHz, CDCl3) δ 7.41–7.17 1H, H-6b), 3.86 (dd, J = 16.5, 8.2 Hz, 3H, H-4′, CH2 PivOAc),
(m, 15H, CH aromatic), 5.05–4.99 (m, 1H, H-2′), 4.95 (d, J = 3.76 (d, J = 9.3 Hz, 1H, H-5′), 3.68 (dd, J = 9.8, 8.7 Hz, 1H, H-4),
11.2 Hz, 1H, CHHBn), 4.78 (d, J = 11.5 Hz, 1H, CHHBn), 4.72 3.53 (t, J = 8.6 Hz, 1H, H-3′), 3.45 (s, 3H, CO2CH3), 3.36–3.29
(d, J = 11.0 Hz, 2H, CHHBn, CHHBn), 4.63 (d, J = 11.5 Hz, 1H, (m, 1H, H-5), 3.24–3.17 (t, J = 9.3 Hz, 1H, H-3), 3.12 (m, J = 9.9,
CHHBn), 4.60–4.55 (m, 2H, CHHBn, H-1′), 4.45 (d, J = 7.7 Hz, 7.7 Hz, 1H, H-2), 1.92 (d, J = 5.6 Hz, 3H, CH3 PivOAc), 1.82 (s,
1H, H-1), 4.38 (dd, J = 11.6, 1.9 Hz, 1H, H-6a), 4.08 (dd, J = 3H, COCH3), 1.77–1.63 (m, 2H, CH2 PivOAc), 1.50 (dd, J = 20.6,
11.6, 6.4 Hz, 1H, H-6b), 3.91 (t, J = 9.1 Hz, 1H, H-4′), 3.84 (d, 13.7 Hz, 1H, CH(CH3)2), 1.00 (d, J = 12.6 Hz, 6H, 2 × CH3
J = 9.5 Hz, 1H, H-5′), 3.70–3.59 (m, 2H, H-4, H-3′), 3.53 (s, 3H, PivOAc), 0.72 (dd, J = 14.4, 7.5 Hz, 12H, C(CH3)2 and
CO2CH3), 3.43 (d, J = 6.9 Hz, 1H, H-4), 3.38–3.31 (m, 1H, H-3), CH(CH3)2), 0.09–0.05 (m, 6H, Si(CH3)2). 13C NMR (126 MHz,
3.27 (dd, J = 9.8, 7.7 Hz, 1H, H-2), 2.10–2.02 (s, 3H, COCH3), CDCl3) δ 128.6, 128.4, 128.5, 128.5, 128.1, 127.9, 127.8, 127.7,
1.94 (s, 3H, COCH3), 1.71–1.59 (m, 1H, CH(CH2)3), 0.93–0.82 127.3, 127.2, 100.2, 96.9, 82.0, 80.8, 79.5, 76.5, 75.5, 75.0, 74.8,
(m, 12H, C(CH3)2 and CH(CH3)2), 0.19 (s, 3H, SiCH3), 0.15 (s, 73.3, 72.8, 68.7, 62.9, 61.5, 52.8, 38.5, 34.2, 31.1, 21.2, 25.2,
3H, SiCH3). 13C NMR (126 MHz, CDCl3) δ 129.0, 128.8, 128.5, 20.9, 20.2, 18.6, −3.0, −1.9. HRMS: m/z: calcd for
128.4, 127.9, 127.7, 127.6, 127.5, 101.3, 96.7, 81.9, 80.9, 79.3, C52H71N3O15SiNa: 1028.4552; found: 1028.4560 [M + Na]+.
78.48, 75.6, 75.1, 75.0, 74.5, 73.0, 72.7, 68.6, 63.3, 62.5, 62.5,
Dimethylthexylsilyl O-(methyl-2-O-(4-acetoxy-
52.4, 33.9, 29.7, 20.8, 20.8, 20.3, 20.25, 19.9, 19.3, 18.5, 18.4,
2,2-dimethylbutanoate)-3-O-benzyl-4-O-(2-methyl-naphthyl)-
17.9. HRMS: m/z: calcd for C46H61N3O13SiNa: 914.3871; found:
β-D-glucopyranosyluronate)-(1→4)-O-2-deoxy-2-azido-
3-O-benzyl-6-O-levulinoyl-β-D-glucopyranoside (29)
914.3879 [M + Na]+.
Dimethylthexylsilyl O-(methyl-2-O-levulinoyl-3,4-O-benzyl-
β-D-glucopyranosyluronate)-(1→4)-O-2-deoxy-2-azido-
3-O-benzyl-6-O-acetyl-β-D-glucopyranoside (24)
Compound 29 (88 mg, 85%) was prepared according to the
general glycosylation procedure from compound 27 (83 mg,
0.11 mmol) and compound 28 (50 mg, 0.09 mmol) catalyzed
Compound 24 (76 mg, 61%) was prepared according to the by TfOH (1.0 µL, 0.01 mmol). 1H NMR (500 MHz, CDCl3)
general glycosylation procedure from compounds 23 (100 mg, δ 7.86–7.73 (m, 2H, CH aromatic), 7.62 (d, J = 14.7 Hz, 1H, CH
0.16 mmol) and 17 (63 mg, 0.13 mmol) catalyzed by TfOH aromatic), 7.51–7.15 (m, 13H, CH aromatic), 5.20–5.10 (t, J =
1
(1.5 µL, 0.016 mmol). H NMR (500 MHz, CDCl3) δ 7.41–7.17 9.7 Hz, 1H, H-2′), 5.03 (dt, J = 14.9, 5.3 Hz, 1H, CHHBn),
(m, 15H, CH aromatic), 5.06–4.99 (m, 1H, H-2′), 4.96 (d, J = 4.84 (t, J = 12.3 Hz, 2H, CHHNAP, CHHBn), 4.80–4.67 (m, 3H,
11.1 Hz, 1H, CHHBn), 4.80–4.64 (m, 4H, CH2 Bn), 4.57 (dd, J = CHHNAP, CHHBn, H-1′), 4.56–4.50 (d, J = 9.3 Hz, 1H, H-1),
9.4, 3.4 Hz, 2H, CHHBn, H-1′), 4.48 (d, J = 7.7 Hz, 1H, H-1), 4.36–4.22 (m, 2H, H-6a, H-6b), 4.15–4.00 (m, 2H, H-5′, H-4′),
4.42 (dd, J = 11.7, 1.8 Hz, 1H, H-6a), 4.14 (dd, J = 11.8, 5.9 Hz, 3.95–3.85 (m, 2H, H-3′, H-4), 3.57 (s, 3H, COOCH3), 3.52–3.46
1H, H-6b), 3.94–3.88 (m, 1H, H-4′), 3.85 (d, J = 9.5 Hz, 1H, (m, 1H, H-5), 3.40–3.26 (m, 2H, H-3, H-2), 2.90–2.71 (m, 2H,
H-5′), 3.68 (dt, J = 17.8, 9.3 Hz, 2H, H-4′, H-5′), 3.59–3.50 (m, CH2 Lev), 2.69–2.53 (m, 2H, CH2 Lev), 2.24–2.19 (s, 3H, CH3
4H, H-5, COOCH3), 3.39–3.32 (m, 1H, H-3), 3.27 (dd, J = 9.8, Lev), 1.99 (s, 3H, COCH3), 1.95–1.83 (m, 2H, CH2 PivOAc), 1.59
7.8 Hz, 1H, H-2), 2.79–2.69 (m, 1H, CH2 Lev), 2.66–2.50 (m, (m, 1H, CH(CH3)2), 1.20 (dd, J = 3.5, 1.3 Hz, 6H, 2 × CH3
2H, CH2 Lev), 2.36–2.27 (m, 1H, CH2 Lev), 2.15 (s, 3H, CH3 PivOAc), 0.91 (d, 12H, C(CH3)2 and CH(CH3)2), 0.24–0.13 (m,
Lev), 2.06 (s, 3H, COCH3), 1.63 (td, J = 13.7, 6.9 Hz, 1H, 6H, Si(CH3)2). 13C NMR (126 MHz, CDCl3) δ 129.0, 128.8,
CH(CH3)2), 0.93–0.82 (m, 12H, C(CH3)2 and CH(CH3)2), 0.19 (s, 128.3, 128.2, 128.0, 127.7, 127.5, 127.1, 126.6, 126.1, 125.7,
3H, SiCH3), 0.15 (s, 3H, SiCH3). 13C NMR (126 MHz, CDCl3) 125.3, 99.9, 96.7, 81.7, 80.6, 79.6, 79.4, 79.3, 76.0, 75.4, 73.1,
δ 128.7, 128.6, 128.3, 128.2, 128.1, 128.0, 127.4, 127.3, 127.2, 75.4, 74.7, 74.5, 72.5, 68.4, 62.6, 61.3, 52.5, 51.9, 38.4, 37.9,
This journal is © The Royal Society of Chemistry 2014
Org. Biomol. Chem., 2014, 12, 2087–2098 | 2095