2306
M. B. Cid et al. / Carbohydrate Research 339 (2004) 2303–2307
OH3) and 3.54–3.45 (m, 4H, 2H6 , H5 and H3 ); 13C
NMR (125MHz, CDCl3): d=166.4, 165.7, 165.1 and
165.0 (4CO), 138.8, 138.4, 138.2 and 138.1 (4C, Bn),
133.9, 133.9, 133.7 and 133.4 (4CHpara), 130.3–127.8
(20CH, Bn and 16CH, Bz), 129.9, 129.9, 129.4 and
C40H46O11: 68.36% C and 6.59% H. Found: 68.35% C
and 6.60% H.
0
0
0
1.2.3.
2,3,4,6-Tetra-O-benzyl-D-galactopyranosyl-
a(1fi3)-D-chiro-inositol (10). This compound has been
prepared from 8 (16.1mg, 0.014mmol) following the
same experimental procedure described for the prepara-
0
129.2 (4C, Bz), 104.7 (C1 ), 82.8 (CH), 79.9 (CH), 79.2
(C2), 76.2 (CH2), 74.9 (CH2), 73.9 (CH), 73.8 (CH2),
73.5 (CH), 72.7 (CH2), 72.5 (CH), 71.9 (CH), 71.2
(CH), 70.2 (CH), 68.7 (CH) and 68.5 (CH2); Anal. Calcd
for C68H62O15: 72.97% C and 5.58% H. Found: 72.89%
C and 5.55% H.
tion of (9). Compound 10 was obtained in quantitative
20
D
yield (10mg). ½a þ 24:0 (c 0.5, CHCl3); 1H NMR
(500MHz, CDCl3): d=7.40–7.20 (m, 20H, 4Bn); 4.93
0
(d, 1H, J=3.9Hz, H1 ); 4.90–4.13 (4 AB syst, 8H);
0
4.13 (m, 2H, H6 or H1 and H5 ); 4.09 (br t, 1H,
Data for the a(1!3) pseudodisaccharide (8):
20
D
½a þ 37:5 (c 0.8, CHCl3); 1H NMR (500MHz,
J=3.3Hz, H6 or H1); 4.07 (dd, 1H, J=9.8 and 3.7Hz,
0 0
H2 ); 3.93 (dd, 1H, J=9.9 and 3.6Hz, H3 ); 3.87–3.80
CDCl3): d=8.13–7.77 (4Hortho, 8H); 7.60–7.10 (m,
20H, 4Bn and 12H, 4Bz); 6.12 (t, 1H, J=10.3Hz, H4);
5.91 (t, 1H, J=3.5Hz, H6); 5.84 (dd, 1H, J=10.4 and
3.5Hz, H5); 5.75 (t, 1H, J=3.5Hz, H1); 4.96 (d, 1H,
0
0
(m, 3H, 2H6 , H4 and H2 or H5); 3.56–3.49 (m, 2H,
H4 and H3); 3.22 (dd, 1H, J=9.5 and 3.4Hz, H2 or
H5) and 2.78 (br s, 5H, 5OH); 13C NMR (125MHz,
CDCl3): d=138.2, 138.1, 137.4 and 137.3 (4C, Bn),
0
J=3.6Hz, H1 ); 4.85–4.10 (4 AB syst, 8H); 4.38 (m,
0
1H, H5 ); 4.34–4.30 (m, 2H, H2 and H3); 3.92 (dd, 1H,
0
128.6–127.5 (20CH, Bn), 99.1 (C1 ), 79.6 (CH), 75.9
0
J=10.4 and 2.9Hz, H3 ); 3.86 (dd, 1H, J=10.2 and
(CH), 74.6 (CH2), 74.5 (CH2), 74.5 (CH), 73.6 (CH2),
72.8 (CH2), 71.5 (CH), 71.2 (CH), 71.1 (CH), 70.9
(CH), 70.7 (CH), 69.7 (CH2), 69.2 (CH) and 67.5
(CH); Anal. Calcd for C40H46O11: 68.36% C and
6.59% H. Found: 68.33% C and 6.54% H.
0
3.6Hz, H2 ); 3.79 (s, 1H, H4 ); 3.39 (dd, 1H, J=9.5
0
0
and 7.8Hz, H6 a) and 3.19 (dd, 1H, J=9.5 and 4.4Hz,
6 b). 13C NMR (125MHz, CDCl3): d=165.9, 165.8,
0
H
165.3 and 165.1 (4CO), 139.1, 138.7, 138.5 and 137.7
(4C, Bn), 133.9, 133.9, 133.5 and 133.3 (4CHpara),
130.4–127.8 (20CH, Bn and 16CH, Bz), 130.3, 129.6,
1.2.4.
D-Galactopyranosyl-a(1fi2)-D-chiro-inositol.
0
129.4 and 129.3 (4C, Bz), 99.6 (C1 H), 80.9 (C3), 79.2
Fagopyritol B1 (2). A slurry of compound 9 (10mg,
0.014mmol) and Pd/C 10% in MeOH/EtOH/water
10:3:1 (2mL) was saturated with a stream of H2 for
30min, and stirred under H2 overnight. The reaction
mixture was filtrated through Celite and the solvent
(CH), 76.0 (CH), 75.4 (CH), 74.7 (CH2), 73.9 (CH2),
73.7 (CH2), 73.3 (CH2), 71.3 (C2), 71.1 (CH), 70.9
(CH), 70.6 (CH), 69.9 (CH2), 69.8 (CH) and 68.8
(CH). Anal. Calcd for C68H62O15+5H2O: 67.60% C
and 5.49% H. Found: 67.69% C and 5.49% H.
evaporated to give 5mg of
1
2
(quantitative).
20
D
½a þ 39:0 (c 0.3, H2O). H NMR (500MHz, D2O):
0
0
1.2.2.
2,3,4,6-Tetra-O-benzyl-D-galactopyranosyl-
solution of
d=4.94 (d, 1H, J=3.8Hz, H1 ); 4.06–4.02 (m, 2H, H5
and H1), 3.88 (t, 1H, J=3.4Hz, H6); 3.84 (d, 1H,
a(1fi2)-D-chiro-inositol (9). To
a
6
0
J=2.7Hz, H4 ); 3.78 (dd, 1H, J=10.3 and 3.7Hz, H3 );
0
(16.1mg, 0.014mmol) in a mixture of dry methanol
and THF (8:1) (2mL), MeONa in MeOH (0.5mL,
1M) was added at room temperature. The solution
was stirred for 30min, whereupon it was quenched with
Amberlite IR-120H+ resin. The solvent and the liquid
0
3.68 (dd, 1H, J=10.2 and 3.8Hz, H2 ); 3.61 (dd, 1H,
J=9.7 and 3.3Hz, H5); 3.64 (dd, 1H, J=9.5 and
0
3.2Hz, H2); 3.55 (m, 2H, H6 ); 3.54 (t, 1H, J=9.5Hz,
H3) and 3.45 (t, 1H, J=9.6Hz, H4). 13C NMR
(125MHz, D2O): d=95.2, 75.1, 72.3, 70.8, 70.6, 70.4,
70.0, 68.9, 68.8, 67.7, 67.3 and 60.5. Anal. Calcd for
C12H22O11: 42.10% C and 6.47% H. Found: 42.08% C
and 6.44% H.
BzOMe were removed by heating at 50ꢁC under vacuum
20
to give 9 (10mg, quantitative); ½a þ 72:0 (c 0.5,
D
MeOH); 1H NMR (500MHz, MeOD): d=7.40–7.20
0
(m, 20H, 4Bn); 4.99 (d, 1H, J=3.6Hz, H1 ); 4.85–4.40
0
(4 AB syst, 8H); 4.41 (m, 1H, H5 ); 4.10–4.05 (m, 2H,
0
0
H3 and H4 ); 4.04 (t, 1H, J=3.3Hz, H1); 4.01 (dd, 1H,
1.2.5. D-Galactopyranosyl-a(1fi3)-D-chiro-inositol.
Fagopyritol A1 (1). This compound has been prepared
0
J=9.9 and 3.6Hz, H2 ); 3.94 (t, 1H, J=3.4Hz, H6);
3.76 (dd, 1H, J=9.5 and 3.2Hz, H2); 3.67 (dd, 1H,
J=9.6 and 3.3Hz, H5); 3.64 (t, 1H, J=9.3Hz, H3);
3.56 (t, 1H, J=9.3Hz, H4); and 3.54–3.52 (m, 2H,
from 10 (16.1mg, 0.014mmol) following the same exper-
imental procedure described for the preparation of 2 to
20
D
yield 10mg of 1 (quantitative). ½a þ 57:5 (c 0.4, H2O);
2H6 ); 13C NMR (125MHz, MeOD): d=138.3, 138.2,
1H NMR (500MHz, D2O): d=5.17 (d, 1H, J=3.9Hz,
0
0
H1 ); 4.08 (t, 1H, J=6.1Hz, H5 ), 3.87–3.81 (m, 3H,
0
H4 , H6 and H1); 3.74 (dd, 1H, J=10.4 and 3.3Hz,
0
137.6 and 137.5 (4C, Bn), 127.8–126.8 (20CH, Bn),
0
95.0 (C1 ), 78.3 (CH), 77.3 (CH), 75.8 (CH), 74.6
0
0
(CH), 74.2 (CH2), 73.2 (CH2), 72.7 (CH), 72.4 (CH2),
71.8 (CH2), 71.4 (CH), 71.0 (CH), 70.5 (CH), 68.7
(CH), 68.5 (CH) and 67.9 (CH2); Anal. Calcd for
H3 ); 3.69–3.66 (m, 2H, H2 and H2); 3.62 (m, 2H, H4
0
and H5) and 3.57–3.53 (m, 3H, 2H6 and H3). 13C
NMR (125MHz, D2O): d=99.1, 80.6, 72.4, 71.3, 70.9,