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Peri et al.
(m, 2H, CO–CH2). 13C NMR (100 MHz, CDCl3): d(ppm) 172.4, 171.1, 117.4, 114.1,
88.2, 85.8, 77.3, 76.7, 74.9, 74.5, 72.7, 63.6, 55.6, 40.0, 31.4, 30.0. MS (MALDI-TOF):
642.7 (M + Na), 658.7 (M + K).
3-O-Allyl-6-benzamidosuccinyl-4-p-methoxybenzyl-b-D-glucopyranosyl sulfox-
ide (3a). To a solution of compound 3 (500 mg, 0.81 mmol) in dry CH2Cl2 (5 mL)
cooled at À 78°C, m-CPBA (123 mL, 1.13 mmol) dissolved in dry CH2Cl2 (5 mL) was
added and the mixture was stirred at this temperature, and TLC (AcOEt/petroleum
ether, 6:4) was used to monitor the reaction. Upon completion, a saturated aqueous
solution of FeSO4 (20 mL) was added, the organic layer was diluted with CH2Cl2
(10 mL) and the biphasic mixture vigorously stirred at rt for 10 min. After usual
workup, the product was purified by FC (eluent: AcOEt/petroleum ether 7:3). Pure
compound 3a was obtained as a mixture of diastereomers 3a’ and 3a@ in almost
equimolar amounts (colourless oil, 343 mg, 82% yield). 3a’: [a]D25°(c 0.1,
CHCl3) + 35.5. 1H NMR (400 MHz, CDCl3): d(ppm) 8.0–7.0 (m, 14 H, Harom),
6.12 (bt, 1H, NH), 6.01 (m, 1H, H-2’), 5.33 (dd, 1H, J = 17.1, 1.5 Hz, H-3’a), 5.20 (dd,
1H, J = 10.4, 1.2 Hz, H-3’b), 4.63 (ABq, 2H, CH2–PMB), 4.55–4.40 (m, 3H, H-1’a,
Ph–CH2–NH), 4.34 (m, 2 H, H-6a and H-1’b), 4.20 (t, 1H, J1–2 = 9.5 Hz, H-2), 4.12
(dd, 1H, J6a–6b = 11.9 Hz, J5–6b = 5.4 Hz, H-6b), 3.95 (d, 1H, J = 9.5 Hz, H-1), 3.79
(s, 3H, OCH3), 3.49 (t, 1H, J = 8.6 Hz, H-3), 3.41 (t, 1H, J = 8.6 Hz, H-4), 3.37 (m,
1H, H-5), 2.69 (m, 2H, COCH2), 2.52 (m, 2H, COCH2). 13C NMR (100 MHz, CDCl3):
d(ppm) 172.5, 171.3, 117.3, 114.1, 93.0, 85.3, 77.7, 75.7, 75.1, 74.7, 73.9, 63.1, 55.6,
44.1, 31.3, 29.8. MS (MALDI-TOF): 661.2 (M + Na), 677.4 (M + K). (M + K).
Anal. Calcd for C34H39NO9S: C, 64.03; H, 6.16; S, 5.03. Found: C, 64.09; H, 6.77;
S, 4.98.
1
3a@: [a]D25°(c 0.1, CHCl3) + 25.6. H NMR (400 MHz, CDCl3): d(ppm) 8.0–7.0
(m, 14 H, Harom), 6.08 (bt, 1H, NH), 5.97 (m, 1H, H-2’), 5.32 (dd, 1H, J = 17.2, 1.4
Hz, H-3’a), 5.20 (dd, 1H, J = 10.5, 1.4 Hz, H-3’b), 4.59 (ABq, 2H, CH2–PMB), 4.50–
4.40 (m, 3H, Ph–CH2–NH, H-1’a), 4.30 (m, 2 H, H-6a, H-1’b), 4.09 (dd, 1H, J6a–
= 11.9 Hz, J5–6b = 4.8 Hz, H-6b), 3.83 (t, 1H, J = 8.7 Hz, H-2), 3.79 (m, 4H, H-1
6b
and OCH3), 3.53 (t, 1H, J = 8.8 Hz, H-3), 3.45 (m, 1H, H-5), 3.18 (t, 1H, J = 9.4 Hz,
H-4), 2.59 (m, 2H, COCH2), 2.48 (m, 2H, COCH2). 13C NMR (100 MHz, CDCl3):
d(ppm) 172.4, 171.1, 117.5, 114.1, 88.4, 85.7, 77.9, 75.6, 75.0, 74.8, 71.01, 62.7, 55.6,
44.1, 31.3, 29.7. MS (MALDI-TOF): 661.5 (M + Na), 677.4 (M + K).
Anal. Calcd for C31H35NO8S: C, 64.01; H, 6.06; S, 5.51. Found: C, 64.18; H, 6.08;
S, 5.53.
Phenyl 3-O-allyl-6-benzamidosuccinyl-1-thio-b-D-glucopyranoside (3b).
A
solution of compound 3 (100 mg, 0.16 mmol) in TFA/CH2Cl2 (1:1) was stirred 1 h
at rt until the hydrolysis was complete. Solvents were evaporated and crude purified by
flash chromatography (AcOEt/petroleum ether, 4:6). Pure compound 3b was recovered
1
as a colorless oil (73.6 mg, 92% yield). [a]D25°(c 0.1, CHCl3) À 18.5. H-NMR (400
MHz, CDCl3): d(ppm) 7.5–7.2 (m, 14 H, Harom), 6.20 (bt, 1H, NH), 5.95 (m, 1H, H-
2’), 5.35 (dd, 1H, J = 17.5, 1.3 Hz, H-3’a), 5.15 (dd, 1H, J = 10.7, 1.6 Hz, H-3’b),
4.45 (ABq, 2H, Ph–CH2–NH), 4.40–4.20 (m, 3H, H-1’a, H-1, 2 H-6), 4.10 (m, 1H,