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¼ 3.2 Hz, 1H, H-1), 5.74 (dd, J ¼ 11.3, 3.2 Hz, 1H, H-2), 5.58 (s, obtained as a white solid. 1H NMR (400 MHz, CDCl3): d 8.58 (s,
1H, CHPh), 4.74 (q, J ¼ 12.9 Hz, 2H, CH2Ph), 4.43 (d, J ¼ 3.2 Hz, 1H, –NH), 7.55–7.50 (m, 2H, ArH), 7.41–7.24 (m, 10H, ArH), 6.84
1H, H-4), 4.34 (d, J ¼ 12.9 Hz, 1H, H-6), 4.28 (dd, J ¼ 11.3, 3.2 Hz, (d, J ¼ 9.7 Hz, 2H, ArH), 6.63 (d, J ¼ 3.2 Hz, 1H, H-1), 5.51 (s, 1H,
1H, H-3), 4.08 (d, J ¼ 12.9 Hz, 1H, H-60), 3.94 (s, 1H, H-5); 13C CHPh), 4.82–4.69 (m, 4H, 2 ꢂ CH2Ph), 4.31–4.22 (m, 3H, H-2, H-
NMR (100 MHz, CDCl3): d 165.6, 160.4, 137.5, 137.4, 133.3, 6, H-60), 4.08 (dd, J ¼ 9.7, 3.2 Hz, 1H, H-3), 4.01 (dd, J ¼ 11.3, 3.2
129.8, 129.4, 129.2, 128.4, 128.38, 128.32, 128.1, 128.0, 126.4, Hz, 1H, H-4), 3.84–3.82 (s, 1H, H-5); 13C NMR (100 MHz, CDCl3):
101.2, 95.0, 73.6, 72.6, 71.7, 69.2, 68.9, 65.4.
d 161.0, 159.2, 138.4, 137.6, 130.2, 129.8, 129.1, 128.3, 128.2,
127.5, 127.4, 127.3, 113.7, 101.2, 95.6, 75.1, 74.6, 74.0, 73.1, 72.0,
69.1, 65.3, 55.3.
Ethyl 3-O-(para-methoxyphenyl)methyl-4:6-O-phenylmethylene-1-
thio-b-D-galactopyranoside 1331
2-Azidoethyl 4:6-O-phenylmethylene-b-d-galactopyranosyl-
(1 / 4)-b-D-glucopyranoside 1635
It was prepared according to the same procedure used to
prepare 12 except for replacing BnCl with PMBCl for the alkyl-
ation reaction. Starting from 4.0 g of 11 (12.8 mmol) and 2.6 mL
of PMBCl (19.2 mmol), 4.58 g of 13 (83%) was obtained as
colorless syrup. 1H NMR (400 MHz, CDCl3): d 7.56 (d, J ¼ 6.8 Hz,
2H, ArH), 7.40–7.31 (m, 5H, ArH), 6.86 (d, J ¼ 8.0 Hz, 2H, ArH),
5.44 (s, 1H, CHPh), 4.69 (q, J ¼ 12.9 Hz, 2H, PhCH2), 4.35 (d, J ¼
8.8 Hz, 1H, H-1), 4.31 (dd, J ¼ 13.2, 1.6 Hz, 1H, H-6), 4.16 (d, J ¼
3.2 Hz, 1H, H-4), 4.04 (t, J ¼ 8.8 Hz, 1H, H-2), 3.97 (dd, J ¼ 13.2,
1.6 Hz, 1H, H-60), 3.79 (s, 3H, –OCH3), 3.47 (dd, J ¼ 8.8, 3.2 Hz,
1H, H-3), 3.41 (s, 1H, H-5), 3.88–3.69 (m, 2H, SCH2CH3), 1.32 (t, J
¼ 7.6 Hz, 3H, SCH2CH3); 13C NMR (100 MHz, CDCl3): d 159.4,
137.9, 130.1, 129.5, 129.0, 128.2, 126.4, 101.3, 85.3, 79.9, 73.5,
71.1, 70.1, 69.4, 68.0, 55.3, 22.9, 15.3.
The solution of 1535 (4.15 g, 10.1 mmol), benzaldehyde dimethyl
acetal (1.82 mL, 12.10 mmol) and CSA (585 mg, 2.5 mmol)
dissolved in anhydrous acetonitrile (50 mL) was stirred at rt
with occasional vacuum application until TLC showed that the
reaction was complete. The reaction was quenched with Et3N
(0.7 mL, 5.04 mmol), and the mixture was diluted with CH2Cl2
(30 mL) and washed with brine. The organic phase was dried
over anhydrous Na2SO4 and concentrated in vacuum. The
residue was puried by ash column chromatography (MeOH–
CH2Cl2, 1 : 9, v/v) to give 16 as a white oppy solid (3.74 g,
1
74.2%). H NMR (400 MHz, CDCl3): d 7.55–7.50 (m, 2H, ArH),
7.38–7.31 (m, 3H, ArH), 5.61 (s, 1H, CHPh), 4.48 (d, J ¼ 7.8 Hz,
1H, H-1), 4.35 (d, J ¼ 7.8 Hz, 1H, H-10), 4.23–4.12 (m, 3H, H-6a0,
H-40, H-6b0), 4.03–3.97 (m, 1H, H-6b), 3.92–3.89 (m, 2H, H-4,
OCH2CH2N3), 3.77–3.70 (m, 1H, OCH2CH2N3), 3.68–3.55 (m,
4H, H-3, H-6a, H-30, H-50), 3.49–3.40 (m, 3H, H-2, OCH2CH2N3),
3.34 (bs, –OH), 3.32–3.25 (m, 2H, H-20, H-5); 13C NMR (100 MHz,
CDCl3): d 138.1, 128.5, 127.6, 126.1, 103.4, 102.9, 100.8, 78.6,
75.9, 75.1, 74.8, 73.4, 72.1, 70.3, 68.8, 68.0, 66.9, 60.3, 50.6.
Ethyl 2-O-benzoyl-3-O-(para-methoxyphenyl)methyl-4:6-O-
phenylmethylene-1-thio-b-D-galactopyranoside 1432
To a solution of 13 (4.5 g, 10.4 mmol) dissolved in anhydrous
DMF was added NaH (275 mg, 11.45 mmol) at 0 ꢁC. Aer 45 min
of stirring, BnBr (1.8ꢁ5 mL, 15.62 mmol) was added to the
reaction mixture at 0 C, and the reaction mixture was stirred
for 6 h. When TLC showed that the reaction was completed, the
ꢁ
reaction was quenched with H2O at 0 C, and the mixture was 2-Azidoethyl 2,3-di-O-phenylmethyl-4:6-O-phenylmethylene-b-
diluted with EtOAc. The aqs layer was extracted with EtOAc (5 ꢂ D-galactopyranosyl-(1 / 4)-2,3,6-tri-O-phenylmethyl-b-D-
20 mL), and the organic phases were combined and dried over glucopyranoside 1736
Na2SO4. The solvent was removed under reduced pressure, and
the residue was puried by ash column chromatography
To the solution of 16 (3.7 g, 7.41 mmol) dissolved in anhydrous
DMF (30 mL) was added NaH (1.07 g, 44.44 mmol) at 0 ꢁC. The
(acetone–hexane 1 : 11, v/v) to obtain 14 (4.38 g, 81%) as
mixture was stirred at 0 ꢁC for 45 min, and then BnBr (6.16 mL,
51.85 mmol) was added. Aer stirring for another 12 h when
TLC showed that the reaction was completed, it was quenched
colorless syrup. 1H NMR (400 MHz, CDCl3): d 7.56 (d, J ¼ 6.5 Hz,
2H, ArH), 7.48–7.26 (m, 10H, ArH), 6.86 (d, J ¼ 8.1 Hz, 2H, ArH),
5.49 (s, 1H, CHPh), 4.88 (q, J ¼ 12.9 Hz, 2H, CH2Ph), 4.71 (s, 2H,
CH2Ph), 4.45 (d, J ¼ 9.7 Hz, 1H, H-1), 4.31 (d, J ¼ 11.3 Hz, 1H, H-
6), 4.14 (d, J ¼ 3.2 Hz, 1H, H-4), 3.97 (d, J ¼ 11.3 Hz, 1H, H-60),
3.89 (t, J ¼ 9.7 Hz, 1H, H-2), 3.81 (s, 3H, –OCH3), 3.59 (dd, J ¼
9.7, 3.2 Hz, 1H, H-3), 3.35 (s, 1H, H-5), 3.93–3.83 (m, 1H,
SCH2CH3), 3.82–3.72 (m, 1H, SCH2CH3), 1.35 (t, J ¼ 6.5 Hz, 3H,
SCH2CH3); 13C NMR (100 MHz, CDCl3): d 159.3, 138.4, 138.0,
130.3, 129.4, 129.1, 128.4, 128.3, 128.2, 127.7, 127.6, 126.6,
113.8, 101.5, 84.4, 80.7, 76.9, 75.7, 74.0, 71.4, 69.8, 69.4, 55.3,
23.8, 15.1; HRMS (ESI TOF): calcd for C30H34NaO6S [M + Na]+ m/
z, 545.1974; found, 545.1972.
with H2O at 0 ꢁC, and the mixture was diluted with EtOAc. The
aqueous layer was extracted with EtOAc (5 ꢂ 25 mL), and the
organic phases were combined and dried over Na2SO4. The
desired product 17 (6.24 g, 89%) was obtained upon ash
column chromatography (acetone–hexane 1 : 10, v/v) of the
condensed product. 1H NMR (400 MHz, CDCl3): d 7.76–7.19 (m,
30H, aromatic), 5.48 (s, 1H, CHPh), 5.21 (d, J ¼ 10.8 Hz, 1H,
CH2Ph), 4.94 (d, J ¼ 11.0 Hz, 1H, CH2Ph), 4.87 (d, J ¼ 11.2 Hz,
1H, CH2Ph), 4.83–4.73 (m, 5H, CH2Ph), 4.56 (d, J ¼ 12.2 Hz, 1H,
CH2Ph), 4.48 (d, J ¼ 7.8 Hz, 1H, H-1), 4.44 (d, J ¼ 7.8 Hz, 1H, H-
10), 4.34 (d, J ¼ 12.0 Hz, 1H, CH2Ph), 4.22 (d, J ¼ 12.2 Hz, 1H, H-
6b0), 4.09–4.03 (m, 2H, H-4, H-6b), 3.99 (t, J ¼ 9.0 Hz, 1H, H-6a0),
3.92–3.84 (m, 2H, H-40, OCH2CH2N3), 3.78 (t, J ¼ 9.3 Hz, 1H, H-
2), 3.76–3.69 (m, 2H, H-6a, OCH2CH2N3), 3.36 (t, J ¼ 9.0 Hz, 1H,
2-O-Benzoyl-3-O-(para-methoxyphenyl)methyl-4:6-O-
phenylmethylene-a-D-galactopyranosyl trichloroacetimidate 9
It was prepared according to the procedure used to prepare 7. H-20), 3.56–3.36 (m, 5H, H-3, H-5, H-30, OCH2CH2N3), 2.96
Starting from 2.15 g of 11 (9.58 mmol), 1.77 g of 9 (81%) was (s, 1H, H-50); 13C NMR (100 MHz, CDCl3): d 138.9; 138.8, 138.6,
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RSC Adv., 2015, 5, 23311–23319 | 23315