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34547615310
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General Procedure for Iminosugar-Annulated Perhydropyrimidines 4 and 5: A solvent-free mixture of oxazolone 1 (2.0 mmol, aldose 2 (2.0 mmol, urea/thiourea 3 (2.0 mmol) and Ce2(SO 4)3 (0.114 g, 10 mol, was taken in a 20-mL vial and subjected to MW irradiation for 8-13 min (Table 1, After completion of the reaction as indicated by TLC, H2O (10 mL) was added to the reaction mixture and stirred for 10 min. The yellowish precipitate thus obtained was washed with H2O to give the crude product which was recrystallized from EtOH to afford a diastereomeric mixture (>94:<6; in the crude products the ratio was >91:<9, as determined by 1H NMR spectroscopy, The product on second recrystallization from EtOH furnished an analytically pure sample of a single diastereomer 4 or 5 Table 1, On the basis of comparison of J values with the literature ones, 24,30-36
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7: C, 52.60; H, 5.24; N, 11.50. Found: C, 52.89; H, 5.59; N, 11.33.
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33
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34547626175
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General Procedure for 5-Aminoperhydropyrimidine-dione Analogues 9 and 10: Compound 4 or 5 (2.0 mmol) was refluxed in H 2SO4-H2o (15 mL, 4:3) for 45 min in an oil bath. The reaction mixture was cooled, the desired products 9 or 10 were precipitated by adding coned NH4OH (specific gravity 0.88) under ice cooling and recrystallized from EtOH to obtain analytically pure samples of 9 and 10, respectively. Characterization Data of Representative Compounds: Compound 9a: pale yellow powder; mp 134-135°C. IR (KBr, 3345, 3011, 1683, 1669, 1605, 1579, 1451 cm -1. 1H NMR (400 MHz, DMSO-d6, D 2O, δ, 2.67 (dd, J6ax,eq, 13.1 Hz, J6ax,7h, 9.8 Hz, 1 H, H-6ax, 3.35 ddd, J7,8, 9.3 Hz, J6ax,7h, 9.8 Hz, J6eq,7h, 3.8 Hz, 1 H, H-7
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6: C, 41.38; H, 5.79; N, 16.09. Found: C, 41.18; H, 5.58; N, 16.21.
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35
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34547628332
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General Procedure for Isolation of Michael Adducts 7a (n, 3, X, O, R, H) and 7j (n, 4, X, S, R, Ph) and Their Conversion into the Corresponding Sugar-Annulated Products 4a and 5d: The procedure followed was the same as described above for the synthesis of 4 and 5 except that the time of MW irradiation in this case was 4-6 min instead of 8-13 min. The adducts 7 were recrystallized from EtOH to give a diastereomeric mixture (>94:<6; in the crude products the ratio was >91:<9, as determined by 1H NMR spectroscopy) which was again recrystallized from EtOH to obtain an analytical sample of 7a and 7j. The adducts 7a and 7j were assigned the anti stereochemistry as their 1H NMR spectra exhibited higher values of coupling constant (JcyclicNCH,acyclicNCH, 9-9 Hz) than that of the very minor (<6, diastereomer syn, JcyclicNCH,acyclicNCH, 4
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7: C, 50.99; H, 5.42; N, 11.89. Found: C, 50.79; H, 5.78; N, 11.63.
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0001891550
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