2216
J. Uenishi, A. Ueda / Tetrahedron: Asymmetry 19 (2008) 2210–2217
138.1, 133.0, 132.6, 130.4, 129.8, 129.7, 128.3, 128.3, 128.2, 128.2,
128.1, 128.0, 127.9, 127.8, 127.7, 127.6, 127.5, 127.5, 127.4, 127.1,
113.4, 109.4, 95.3, 85.6, 85.5, 85.1, 82.0, 82.0, 77.6, 75.6, 75.3, 75.0,
74.7, 73.2, 68.6, 64.6, 63.5, 26.6, 25.3. IR (film) cmꢀ1: 2870, 1723,
1602, 1496, 1453, 1383, 1273, 1070, 1027, 871, 752, 711. MS
(FAB) m/z: 973 (M+Na)+. HR-MS (FAB) m/z: 973.3771 (calcd for
C57H58O13Na: 973.3775).
4.4.3. (1,4,6-Tri-O-benzoyl-b-
2,3,4,6-tetra-O-benzyl- -glucopyranoside 14
To a solution of oxalyl chloride (15.9 L, 182
(1.5 mL) was dropped DMSO (25.8 L, 364
(0.2 mL) at ꢀ78 °C, and the mixture was stirred for 15 min at the
same temperature. Then, a solution of 13 (61.5 mg, 60.6 mol) in
D-erythro-2,3-hexodiulofuranosyl)
a-D
l
lmol) in CH2Cl2
l
lmol) in CH2Cl2
l
CH2Cl2 (1.0 mL) was added dropwise and the whole mixture was
stirred for 1 h at ꢀ78 °C prior to addition of triethylamine
4.4. Synthesis of (+)-sucrose
(101 lL, 727 lmol). Satd. aqueous NH4Cl solution was added and
the mixture was extracted with EtOAc, washed with water, brine,
dried over MgSO4, and concentrated in vacuo. The residue was
purified by flash chromatography on silica gel eluted with 15%
EtOAc in hexane to give 14 (58.5 mg) in 95% yield. Colorless syrup.
4.4.1. (1,6-Di-O-benzoyl-b-
benzyl- -glucopyranoside 12
A methanol (6 mL) solution of 11b
toluenesulfonic acid monohydrate (90.6 mg, 477
D-psicofuranosyl) 2,3,4,6-tetra-O-
a-D
a
(152 mg, 159
lmol) and p-
lmol) was stirred
Rf = 0.50 (30% EtOAc in hexane). ½a D23
ꢂ
¼ þ98:5 (c 0.68, CHCl3). 1H
for 42 h at room temperature. Satd aqueous NaHCO3 solution was
added and it was extracted with CHCl3, and washed with water.
The organic extracts were dried over MgSO4 and concentrated to
dryness, and then purified by silica gel flash chromatography
eluted with 35% EtOAc in hexane to give 12 (104 mg) in 72% yield.
NMR (300 MHz, CDCl3) d: 8.06–8.00 (6H, m), 7.65–7.56 (2H, m),
0
0
7.48–7.16 (27H, m), 6.33 (1H, d, J4 ,5 = 8.3 Hz, H-4), 5.69 (1H, d,
J1,2 = 3.9 Hz, H-1), 4.95 (1H, d, J = 10.6 Hz), 4.89–4.53 (10H, m),
4.46 (1H, d, J = 11.7 Hz), 4.46 (1H, d, J = 11.9 Hz), 3.94 (1H, dd,
J2,3 = J3,4 = 9.7 Hz, H-3), 3.82 (1H, dd, J3,4 = 9.7, J4,5 = 9.2 Hz, H-4),
3.79 (1H, dd, J6a,6b = 11.0, J5,6a = 2.0 Hz, H-6a), 3.63 (1H, ddd,
J4,5 = 9.2, J5,6a = 2.0, J5,6b = 1.8 Hz, H-5), 3.52 (1H, dd, J6a,6b = 11.0,
J5,6b = 1.8 Hz, H-6b), 3.39 (1H, dd, J2,3 = 9.7, J1,2 = 3.9 Hz, H-2). 13C
NMR (75 MHz, CDCl3) d: 205.3, 166.0, 165.0, 164.8, 138.5, 138.2,
137.5, 133.8, 133.3, 133.2, 129.9, 129.7, 129.6, 129.3, 129.1, 128.5,
128.4, 128.4, 128.3, 128.2, 128.2, 128.1, 127.9, 127.8, 127.7, 127.4,
97.7, 90.1, 81.1, 78.4, 75.9, 75.6, 75.2, 73.4, 73.4, 72.8, 71.6, 69.4,
67.4, 66.7, 63.2. IR (film) cmꢀ1: 2925, 1784, 1730, 1601, 1495,
1453, 1268, 1091, 709. MS (FAB) m/z: 1035 (M+Na)+. HR-MS
(FAB) m/z: 1035.3564 (calcd for C61H56O14Na: 1035.3568).
Colorless syrup. Rf = 0.29 (40% EtOAc in hexane). ½a D22
¼ þ55:5 (c
ꢂ
1.03, CHCl3). 1H NMR (300 MHz, CDCl3) d: 8.08–8.02 (4H, m),
7.60–7.11 (26H, m), 5.52 (1H, d, J1,2 = 3.5 Hz, H-1), 4.84–4.79 (3H,
m), 4.69–4.58 (4H, m), 4.55 (1H, d, J = 11.9 Hz), 4.53 (1H, d,
J = 11.6 Hz), 4.46 (1H, d, J = 11.9 Hz), 4.45 (1H, d, J = 11.0 Hz),
4.41–4.33 (3H, m), 4.30–4.25 (2H, m), 4.05 (1H, ddd, J4,5 = 10.1,
J5,6b = 6.2, J5,6a = 1.7 Hz, H-5), 3.93 (1H, t, J = 9.3 Hz), 3.70 (1H, dd,
J6a,6b = 10.1, J5,6a = 1.7 Hz, H-6a), 3.53 (1H, dd, J6a,6b = 10.1,
J5,6b = 6.2 Hz, H-6b), 3.50 (1H, dd, J2,3 = 9.7, J1,2 = 3.5 Hz, H-2), 3.42
(1H, dd, J = 10.0, 8.9 Hz), 2.60 (1H, d, J = 6.6 Hz, OH). 13C NMR
(75 MHz, CDCl3) d: 167.0, 166.3, 138.5, 137.9, 137.7, 137.4, 133.0,
129.9, 129.8, 129.6, 128.3, 128.3, 128.2, 128.1, 128.0, 127.9,
127.8, 127.8, 127.7, 127.6, 127.5, 107.3, 89.6, 81.9, 81.5, 79.0,
77.7, 75.5, 74.9, 73.7, 73.4, 72.5, 71.4, 70.9, 69.0, 65.7, 63.6. IR (film)
cmꢀ1: 3458, 2922, 1715, 1601, 1495, 1453, 1275, 1068. MS (FAB)
m/z: 933 (M+Na)+. HR-MS (FAB) m/z: 933.3456 (calcd for
C54H54O13Na: 933.3462).
4.4.4. (1,4,6-Tri-O-benzoyl-b-
benzyl- -glucopyranoside 15
To a stirred solution of 14 (58.5 mg, 57.7
CH2Cl2 (1:1, 3.0 mL) was added NaBH4 (4.4 mg, 115
D-fructofuranosyl) 2,3,4,6-tetra-O-
a-D
lmol) in MeOH and
lmol) at 0 °C
and the mixture was stirred for 30 min at the same temperature.
The mixture was diluted with water and extracted with EtOAc.
Organic extract was washed with water and brine and dried over
MgSO4. The residue was purified by flash chromatography on silica
gel (eluent: 15% EtOAc in hexane) to give 15 (55.6 mg) in 95% yield.
4.4.2. (1,4,6-Tri-O-benzoyl-b-
benzyl- -glucopyranoside 13
A stirred solution of 12 (94.2 mg, 103
(IV) oxide (25.6 mg, 103 mol) in MeOH (6.9 mL) was heated at re-
flux temperature for 45 min. Then, BzCl (119 L, 1.03 mmol) and
triethylamine (143 L, 1.03 mmol) were added to the mixture at
D-psicofuranosyl) 2,3,4,6-tetra-O-
a-D
lmol) and di-n-butyltin
Colorless syrup. Rf = 0.44 (30% EtOAc in hexane). ½a D21
¼ þ39:2 (c
ꢂ
l
1.00, CHCl3). 1H NMR (300 MHz, CDCl3) d: 8.05–7.92 (6H, m),
l
7.56–7.48 (2H, m), 7.45–7.31 (7H, m), 7.28–7.09 (20H, m), 5.64
0
0
l
(1H, d, J1,2 = 3.9 Hz, H-1), 5.59 (1H, d, J4 ,5 = 7.2 Hz, H-40), 4.84
(1H, d, J = 10.8 Hz), 4.81–4.73 (2H, m), 4.69–4.34 (11H, m), 4.13
(1H, ddd, J4,5 = 9.9, J5,6b = 4.4, J5,6a = 2.1 Hz, H-5), 3.95 (1H, dd,
0 °C successively, and stirred for 10 min at the same temperature,
then evaporated under vacuum. The residual solid was dissolved
in a minimum amount of chloroform and purified by silica gel flash
chromatography, eluted with 15% EtOAc in hexane to yield 13
(61.5 mg) in 59% yield. Colorless syrup. Rf = 0.61 (40% EtOAc in hex-
0
J2,3 = 9.4, J3,4 = 9.2 Hz, H-3), 3.79 (1H, d, J3 ,OH = 9.4 Hz, OH), 3.64
(1H, dd, J6a,6b = 10.7, J5,6a = 2.1 Hz, H-6a), 3.60 (1H, dd,
J6a,6b = 10.7, J5,6b = 4.4 Hz, H-6b), 3.55 (1H, dd, J4,5 = 9.9,
J3,4 = 9.2 Hz, H-4), 3.51 (1H, dd, J2,3 = 9.9, J1,2 = 3.9 Hz, H-2). 13C
NMR (75 MHz, CDCl3) d: 166.0, 165.9, 165.7, 138.4, 138.0, 137.6,
137.4, 133.4, 133.2, 132.9, 129.8, 129.7, 129.7, 129.6, 129.5,
129.0, 128.4, 128.4, 128.3, 128.2, 128.1, 127.9, 127.9, 127.8,
127.7, 127.6, 104.4, 91.2, 81.7, 78.6, 77.9, 77.9, 77.5, 77.1, 75.6,
75.0, 73.4, 73.2, 71.5, 68.3, 64.8, 64.1. IR (film) cmꢀ1: 3459, 2925,
1730, 1602, 1495, 1453, 1272, 1070, 698. MS (FAB) m/z: 1037
(M+Na)+. HR-MS (FAB) m/z: 1037.3733 (calcd for C61H58O14Na:
1037.3724).
ane). ½a 2D3
ꢂ
¼ þ37:5 (c 0.99, CHCl3). 1H NMR (300 MHz, CDCl3) d:
8.10-8.06 (4H, m), 8.02–7.98 (2H, m), 7.61–7.42 (6H, m), 7.34–
7.12 (23H, m), 5.55 (1H, d, J1,2 = 3.5 Hz, H-1), 5.49 (1H, dd,
J3 ,4 = 5.4, J4 ,5 = 4.7 Hz, H-40), 4.90 (1H, dd, J3 ,OH = 5.5, J3 ,4 = 5.4 Hz,
H-30), 4.84–4.79 (3H, m), 4.74–4.44 (10H, m), 4.20 (1H, ddd,
J4,5 = 9.8, J5,6b = 6.8, J5,6a = 1.5 Hz, H-5), 3.99 (1H, dd, J2,3 = 9.8,
0
0
0
0
0
0
0
0
J3,4 = 9.2 Hz, H-3), 3.93 (1H, d, J3 ,OH = 5.5 Hz, OH), 3.74 (1H, dd,
J6a,6b = 9.8, J5,6a = 1.5 Hz, H-6a), 3.50 (1H, dd, J6a,6b = 9.8,
J5,6b = 6.8 Hz, H-6b), 3.48 (1H, dd, J2,3 = 9.8, J1,2 = 3.5 Hz, H-2), 3.38
(1H, dd, J4,5 = 9.8, J3,4 = 9.2 Hz, H-4). 13C NMR (75 MHz, CDCl3) d:
166.8, 166.1, 165.7, 138.5, 137.9, 137.8, 137.2, 133.4, 133.0,
132.8, 130.0, 129.9, 129.8, 129.7, 129.4, 129.2, 128.5, 128.4,
128.3, 128.2, 128.0, 127.9, 127.9, 127.9, 127.8, 127.7, 127.5,
107.8, 89.6, 82.0, 79.2, 78.8, 77.7, 75.5, 74.9, 73.4, 73.4, 72.5,
72.2, 70.9, 69.0, 65.2, 63.5. IR (film) cmꢀ1: 3440, 3030, 2923,
1723, 1601, 1495, 1452, 1315, 1271, 1070, 1026, 750, 710. MS
(FAB) m/z: 1037 (M+Na)+. HR-MS (FAB) m/z: 1037.3716 (calcd for
C61H58O14Na: 1037.3724).
4.4.5. (1,3,4,6-Tetra-O-acetyl-b-D-fructofuranosyl) 2,3,4,6-tetra-
O-acetyl- -glucopyranoside 16
a-D
Metal Na (approximately 60 mg) was added to liquid ammonia
(2 mL) at ꢀ78 °C. To the resultant dark blue solution was added 15
(54.2 mg, 53.3 mmol) in THF (2 mL) solution and stirred for 30 min
at the same temperature. The reaction was quenched with acetic
acid (0.5 mL) and MeOH (2 mL) at ꢀ78 °C and evaporated. The
residue obtained after removal of the solvent was dissolved in