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Vol. 52, No. 2
126.0, 102.6, 78.5, 78.4, 75.2, 71.7, 69.0, 62.8, 32.6, 32.1; FAB-MS m/z: C12H17NO6·1/4H2O: C, 52.26; H, 6.40; N, 5.08%.
299 (Mϩ1)ϩ; Anal. Found: C, 60.24; H, 7.46. Calcd for C15H22O6: C, 60.39;
H, 7.43%.
Isobutyl b-D-Glucopyranoside (15) A mixture of 5 (0.5 g, 1.66 mmol),
isobutanol (1.23 g, 16.6 mmol) and b-glucosidase 20 mg (70 unit) in phos-
4-Phenylbutyl b-D-Glucopyranoside (10) A mixture of 5 (1 g, 3.32 phate buffer (pH 5, 17 ml) was incubated for 24 h at 30 °C. After the reaction
mmol), 4-phenylbutanol (496 mg, 3.30 mmol) and b-glucosidase 5 mg (17 mixture was boiled for 5 min and evaporated under reduced pressure, the
unit) in phosphate buffer (pH 5, 34 ml) was incubated for 18 h at 30 °C.
residue was chromatographed on silica gel (20 g, CHCl3/MeOHϭ40 : 1) to
After the reaction mixture was boiled for 5 min and evaporated under re- afford 15 (133 mg, 34%) as colorless crystals. 15: mp 111—114 °C; [a]D27
duced pressure, the residue was chromatographed on silica gel (40 g, CHCl3/ Ϫ39.1° (cϭ0.5, H2O); IR (KBr): 3392, 2912, 1087, 1062, 1038 cmϪ1, H-
1
MeOHϭ30 : 1) to afford 10 (139 mg, 13%). 10: [a]D29 Ϫ27.0° (cϭ0.59, NMR (DMSO-d6): d: 0.87 (3H, d, Jϭ6.4 Hz), 0.88 (3H, d, Jϭ6.4 Hz), 3.17
1
MeOH); IR (KBr): 3344, 2936, 2874, 1079, 1028 cmϪ1, H-NMR (DMSO- (1H, dd, Jϭ6.8, 9.3 Hz), 3.54 (1H, dd, Jϭ6.8, 9.3 Hz), 3.66 (1H, dd, Jϭ5.6,
d6): d: 2.58 (2H, t, Jϭ7.3 Hz), 3.66 (1H, dq, Jϭ1.5, 5.9 Hz), 3.78 (1H, q, 10.5 Hz), 4.09 (1H, d, Jϭ7.8 Hz), 4.89 (1H, dd, Jϭ4.6, 12.4 Hz), 4.94 (1H,
Jϭ6.6 Hz), 4.09 (1H, d, Jϭ7.8 Hz), 4.44 (1H, t, Jϭ5.9 Hz), 4.87 (2H, dd, q, Jϭ4.9 Hz); 13C-NMR (pyridine-d5): d: 104.6, 78.4, 78.2, 76.4, 75.0, 71.6,
Jϭ4.6, 11 Hz), 4.93 (1H, d, Jϭ4.9 Hz), 7.14—7.28 (5H, m); 13C-NMR (pyri- 62.7, 29.0, 19.6, 19.6; FAB-MS m/z: 237 (Mϩ1)ϩ; Anal. Found: C, 50.58;
dine-d5): d: 142.8, 128.8, 128.8, 128.6, 128.6, 126.0, 104.6, 78.6, 78.5, 75.2, H, 8.59. Calcd for C10H20O6: C, 50.83; H, 8.53%.
71.7, 69.6, 62.9, 36.0, 30.0, 28.5; FAB-MS m/z: 313 (Mϩ1)ϩ; Anal. Found:
C, 61.02; H, 7.92. Calcd for: C16H24O6; C, 61.52; H, 7.74%.
Isopentyl b-D-Glucopyranoside (16) A mixture of 5 (1 g, 3.32 mmol),
isopentanol (295 mg, 3.35 mmol) and b-glucosidase 100 mg (340 unit) in
5-Phenylpentyl b-D-Glucopyranoside (11) A mixture of 5 (2 g, 6.64 phosphate buffer (pH 5, 34 ml) was incubated for 24 h at 30 °C. After the re-
mmol), 5-phenylpentanol (558 mg, 3.40 mmol) and b-glucosidase 8 mg (27 action mixture was boiled for 5 min and evaporated under reduced pressure,
unit) in phosphate buffer (pH 5, 68 ml) was incubated for 24 h at 30 °C.
the residue was chromatographed on silica gel (40 g, CHCl3/MeOHϭ20 : 1)
After the reaction mixture was boiled for 5 min and evaporated under re- to afford 16 (136 mg, 16%) as colorless crystals. 16: mp 86—87 °C; [a]D27
duced pressure, the residue was chromatographed on silica gel (80 g, CHCl3/ Ϫ37.3° (cϭ0.5, H2O); IR (KBr): 3425, 2945, 1075, 1030 cmϪ1, H-NMR
1
MeOHϭ30 : 1) to afford 11 (236 mg, 11%) as colorless crystals. 11: mp (DMSO-d6): d: 0.87 (6H, d, Jϭ6.8 Hz), 1.42 (2H, q, Jϭ6.8 Hz), 1.68 (1H,
65—66 °C; [a]D28 Ϫ25.3° (cϭ0.9, MeOH); IR (KBr): 3414, 2934, 1075, septet, Jϭ6.8 Hz), 3.79 (1H, dt, Jϭ7.1 Hz), 4.09 (1H, d, Jϭ7.8 Hz), 4.46
1
1035 cmϪ1, H-NMR (DMSO-d6): d: 2.56 (2H, t, Jϭ7.6 Hz), 3.66 (1H, dq, (1H, t, Jϭ5.9 Hz), 4.88 (2H, dd, Jϭ4.9, 12.2 Hz), 4.92 (1H, q, Jϭ4.9 Hz);
Jϭ1.5, 5.9 Hz), 3.75 (1H, q, Jϭ6.8 Hz), 4.09 (1H, d, Jϭ7.8 Hz), 4.45 (1H, t, 13C-NMR (pyridine-d5): d: 104.4, 78.4, 78.2, 74.9, 71.6, 68.2, 62.7, 38.9,
Jϭ5.9 Hz), 4.88 (2H, dd, Jϭ4.9, 12.2 Hz), 4.92 (1H, d, Jϭ4.9 Hz), 7.14— 25.2, 22.8, 22.8; FAB-MS m/z: 251 (Mϩ1)ϩ; Anal. Found: C, 52.40; H,
7.28 (5H, m); 13C-NMR (pyridine-d5): d: 142.8, 128.7, 128.7, 128.6, 128.6,
8.89. Calcd for C11H22O6: C, 52.78; H, 8.86%.
4-Methoxycinnamyl b-D-Glucopyranoside (17) A mixture of 5 (1 g,
126.0, 104.4, 78.4, 78.2, 75.0, 71.6, 69.7, 62.8, 36.1, 31.7, 30.1, 26.1; FAB-
MS m/z: 327 (Mϩ1)ϩ; Anal. Found: C, 62.33; H, 8.30. Calcd for C17H26O6: 3.32 mmol), 4-methoxycinnamylalcohol (1.10 g, 6.71 mmol) and b-glucosi-
C, 62.56; H, 8.03%.
dase 120 mg (408 unit) in phosphate buffer (pH 5, 34 ml) was incubated for
6-Phenylhexyl b-D-Glucopyranoside (12) A mixture of 5 (2 g, 6.64 24 h at 30 °C. After the reaction mixture was boiled for 5 min and evaporated
mmol), 6-phenylhexanol (594 mg, 3.33 mmol) and b-glucosidase 4 mg (14 under reduced pressure, the residue was chromatographed on silica gel (40 g,
unit) in phosphate buffer (pH 5, 68 ml) was incubated for 24 h at 30 °C.
CHCl3/MeOHϭ20 : 1) to afford 17 (114 mg, 11%) as colorless crystals. 17:
After the reaction mixture was boiled for 5 min and evaporated under re- mp 132—134 °C; [a]D28 Ϫ53.3° (cϭ0.34, MeOH); IR (KBr): 3350, 2936,
duced pressure, the residue was chromatographed on silica gel (80 g, CHCl3/ 1085, 1019 cmϪ1, H-NMR (pyridine-d5): d: 3.68 (3H, s), 3.93—4.00 (1H,
1
MeOHϭ30 : 1) to afford 12 (114 mg, 5%) as colorless crystals. 12: mp 50—
m), 4.11 (1H, t, Jϭ8 Hz), 4.23—4.30 (2H, m), 4.39 (1H, dd, Jϭ5.3, 11.7
52 °C; [a]D29 Ϫ24.4° (cϭ0.44, MeOH); IR (KBr): 3398, 2932, 2860, 1076, Hz), 4.47 (1H, dd, Jϭ6.3, 12.7 Hz), 4.58 (1H, dd, Jϭ2.0, 11.7 Hz), 4.75 (1H,
1031 cmϪ1
,
1H-NMR (DMSO-d6): d: 2.56 (2H, t, Jϭ8 Hz), 3.66 (1H, q, dd, Jϭ5.6, 12.5 Hz), 4.97 (1H, d, Jϭ7.3 Hz), 5.73 (4H, br s), 6.37 (1H, dt,
Jϭ5.9 Hz), 3.74 (1H, q, Jϭ6.6 Hz), 4.09 (1H, d, Jϭ7.8 Hz), 4.59 (1H, t, Jϭ5.8, 15.8 Hz), 6.73 (1H, d, Jϭ15.8 Hz), 6.95 (2H, d, Jϭ8.3 Hz), 7.38 (2H,
Jϭ5.9 Hz), 4.88 (2H, dd, Jϭ4.9, 11.7 Hz), 4.92 (1H, d, Jϭ5.3 Hz), 7.13— d, Jϭ8.3 Hz); 13C-NMR (pyridine-d5): d: 159.8, 132.0, 130.1, 128.1, 128.1,
7.28 (5H, m); 13C-NMR (pyridine-d5): d: 143.0, 128.7, 128.7, 128.6, 128.6,
126.0, 104.5, 78.4, 78.3, 75.1, 71.6, 69.7, 62.7, 35.9, 31.6, 30.1, 29.2, 26.1;
FAB-MS m/z: 341 (Mϩ1)ϩ; Anal. Found: C, 62.97; H, 8.62. Calcd for
C18H28O6: C, 63.51; H, 8.29%.
124.5, 114.5, 114.5, 103.8, 78.5, 78.5, 75.2, 71.7, 70.0, 62.8, 55.2; HR-MS
(FAB-MS) m/z: 327.1483; Calcd for C14H21O6 m/z: 327.1444 (Mϩ1)ϩ; Anal.
Found: C, 57.66; H, 6.72. Calcd for C16H22O7·1/3H2O: C, 57.82; H, 6.87%.
Isopropyl d-D-Glucopyranoside (18) A mixture of 5 (1 g, 3.32 mmol),
2-Furfuryl b-D-Glucopyranoside (13) A mixture of 5 (1 g, 3.32 mmol), isopropanol (2 g, 33.2 mmol) and b-glucosidase 40 mg (145 unit) in phos-
furfuryl alcohol (1.31 g, 13.4 mmol) and b-glucosidase 100 mg (340 unit) in phate buffer (pH 5, 34 ml) was incubated for 24 h at 30 °C. After the reaction
phosphate buffer (pH 5, 34 ml) was incubated for 27 h at 30 °C. After the re- mixture was boiled for 5 min and evaporated under reduced pressure, the
action mixture was boiled for 5 min and evaporated under reduced pressure, residue was chromatographed on silica gel (40 g, CHCl3/MeOHϭ20 : 1) to
the residue was chromatographed on silica gel (40 g, CHCl3/MeOHϭ30 : 1) afford 18 (147 mg, 20%) as colorless crystals. 18: mp 126—127 °C; [a]D27
1
to afford 13 (269 mg, 31%) as colorless crystals. 13: mp 109—110 °C; [a]D23
Ϫ35.5° (cϭ0.5, H2O); IR (KBr): 3390, 2950, 1080, 1040, 1030 cmϪ1, H-
Ϫ72.0° (cϭ0.51, MeOH); IR (KBr): 3414, 2920, 1071, 1015 cmϪ1
,
1H- NMR (DMSO-d6): d: 1.10 (3H, d, Jϭ6.3 Hz), 1.14 (3H, d, Jϭ5.9 Hz), 3.42
NMR (DMSO-d6): d: 3.46 (1H, dt, Jϭ5.9 Hz), 3.70 (1H, d, Jϭ6.3 Hz), 4.21 (1H, quintet, Jϭ5.9 Hz), 3.65 (1H, dq, Jϭ1.7, 5.6 Hz), 3.90 (1H, dq, Jϭ
(1H, d, Jϭ7.8 Hz), 4.52 (1H, dd, Jϭ3, 12.2 Hz), 4.74 (1H, d, Jϭ12.7 Hz), 6.4 Hz), 4.16 (1H, d, Jϭ7.8 Hz), 4.43 (1H, t, Jϭ5.6 Hz), 4.86 (2H, d,
4.92 (1H, dd, Jϭ4.9, 13.8 Hz), 5.05 (1H, d, Jϭ5.4 Hz), 6.43 (1H, d, Jϭ Jϭ4.9 Hz), 4.89 (1H, q, Jϭ4.9 Hz); 13C-NMR (pyridine-d5): d: 102.4, 78.4,
3 Hz), 6.45 (1H, d, Jϭ3 Hz), 7.64 (1H, d, Jϭ1 Hz); 13C-NMR (pyridine-d5): 78.2, 75.1, 71.6, 70.9, 62.8, 24.0, 22.1; FAB-MS m/z: 223 (Mϩ1)ϩ; Anal.
d: 152.1, 143.2, 110.9, 110.0, 103.6, 78.7, 78.5, 75.1, 71.7, 63.0, 62.8; HR-
Found: C, 48.22; H, 8.17. Calcd for C9H18O6: C, 48.64; H, 8.16%.
Cyclohexyl b-D-Glucopyranoside (19) A mixture of 5 (2 g, 6.64
MS (FAB-MS) m/z: 261.0936; Calcd for C11H17O7 m/z: 261.0974 (Mϩ1)ϩ;
Anal. Found: C, 49.62; H, 6.17. Calcd for C11H16O7·1/3H2O: C, 49.62; H, mmol), cyclohexanol (0.673 g, 6.72 mmol) and b-glucosidase 300 mg (1020
6.31%.
2-Pyridylmethyl b-D-Glucopyranoside (14) A mixture of 5 (1 g, 3.32
unit) in phosphate buffer (pH 5, 68 ml) was incubated for 24 h at 30 °C.
After the reaction mixture was boiled for 5 min and evaporated under re-
mmol), 2-pyridinemethanol (1.82 g, 16.7 mmol) and b-glucosidase 40 mg duced pressure, the residue was chromatographed on silica gel (80 g, CHCl3/
(136 unit) in phosphate buffer (pH 5, 34 ml) was incubated for 22 h at 30 °C. MeOHϭ30 : 1) to afford 19 (77 mg, 4%) as colorless crystals. 19: mp 128—
After the reaction mixture was boiled for 5 min and evaporated under re- 130 °C; [a]D26 Ϫ46.3° (cϭ0.32, MeOH); IR (KBr): 3378, 2934, 1075, 1025
duced pressure, the residue was chromatographed on silica gel (40 g, CHCl3/ cmϪ1 1H-NMR (DMSO-d6): d: 4.21 (1H, d, Jϭ7.8 Hz), 4.41 (1H, t, Jϭ
MeOHϭ20 : 1) to afford 14 (216 mg, 24%) as colorless crystals. 14: mp
5.9 Hz), 4.83 (1H, d, Jϭ4.9 Hz), 4.86 (2H, dd, Jϭ4.4, 9.3 Hz); 13C-NMR
114—116 °C; [a]D26 Ϫ42.4° (cϭ0.45, MeOH); IR (KBr): 3340, 2928, 1081, (pyridine-d5): d: 102.6, 78.7, 78.5, 76.6, 75.3, 71.8, 63.0, 34.3, 32.4, 26.2,
1058, 1040 cmϪ1 1H-NMR (DMSO-d6): d: 3.52 (1H, quintet, Jϭ5.9 Hz), 24.5, 24.3; HR-MS (FAB-MS) m/z: 263.1523; Calcd for C12H23O6 m/z:
3.75 (1H, dq, Jϭ1.5, 5.9 Hz), 4.35 (1H, d, Jϭ7.8 Hz), 4.59 (1H, t, Jϭ 263.1495 (Mϩ1)ϩ; Anal. Found: C, 53.82; H, 8.50. Calcd for C12H22O6·
,
,
5.9 Hz), 4.74 (1H, d, Jϭ13.7 Hz), 4.96 (2H, dd, Jϭ4.5, 8.4 Hz), 5.03 (1H, d,
Jϭ4.9 Hz), 5.30 (1H, d, Jϭ4.4 Hz), 7.34 (1H, dd, Jϭ8, 4 Hz), 7.66 (1H, d,
1/3H2O: C, 53.72; H,8.51%.
Diastereomeric Mixture of 1-Phenylethyl b-D-Glucopyranoside (20)
Jϭ8 Hz), 7.86 (1H, dt, Jϭ2, 8 Hz), 8.56 (1H, d, Jϭ4 Hz); 13C-NMR (pyri- A mixture of 5 (1 g, 3.32 mmol), 1-phenylethanol (405 mg, 3.32 mmol) and
dine-d5): d: 159.0, 149.2, 136.6, 122.5, 121.8, 104.4, 78.6, 78.5, 75.3, 71.9,
71.5, 62.7; HR-MS (FAB-MS) m/z: 272.1119; Calcd. for C12H18NO6 m/z: bated for 32 h at 30 °C. After the reaction mixture was boiled for 5 min and
272.1134 (Mϩ1)ϩ; Anal. Found: C, 52.50; H, 6.40; N, 5.01. Calcd for
evaporated under reduced pressure, the residue was chromatographed on sil-
b-glucosidase 100 mg (340 unit) in phosphate buffer (pH 5, 34 ml) was incu-