514
P.W. Needs, G. Williamson / Carbohydrate Research 330 (2001) 511–515
4.27 (d, 1 H, J5%%,4%% 9.2 Hz, H-5%% (7-sub-
stituent)), 4.19 (d, 1 H, J5%%,4%% 9.6 Hz, H-5%%
(4%-substituent)), 3.74 and 3.73 (2×s, 2×3 H,
2×COOCH3), 2.10, 2.08, 2.07, 2×2.06, 2.05
(6 s, 6×3 H, 6×COCH3). APIMS: m/z 887
[M+H]+.
0.41 mmol of pure 10) was sonicated into
suspension in MeOH (30 mL), and cooled to
1 °C. Aq LiOH (30 mL, 0.5 M), precooled to
1 °C was added, and the mixture stirred at
1 °C for 16 h. Dowex 50W resin (H+ form, 20
mL) was added; after stirring for a further 10
min, the solution was eluted through a 5×2
cm column of Dowex, and the latter was
washed with MeOH. The combined eluate was
evaporated to dryness, and the residue dis-
solved in MeOH (4 mL). The material (4×1
mL) was purified by preparative HPLC (see
above), and purity was checked by analytical
HPLC. Yield 120 mg, 67%. 1H NMR
(CD3OD): l 8.19 (s, 1 H, H-2), 8.15 (d, 1 H,
J5,6 9.0 Hz, H-5), 7.38 (AA%BB% system, 2 H,
J2%,3% 8.4 Hz, H-2%, H-6%), 7.25 (d, 1 H, J8,6 2.4
Hz, H-8), 7.22 (dd, 1 H, H-6), 6.84 (AA%BB%
system, 2 H, H-3%, H-5%), 5.17 (d, 1 H, J1,2 7.2
Hz, H-1%%), 4.01 (d, 1 H, J5,4 10.0 Hz, H-5%%),
3.4–3.7 (m, 3 H, H-2%%, H-3%%, H-4%%). ESMS:
m/z 429 [M−H]−. FABMS (glycerol matrix):
m/z [M−H]−. Anal. Calcd 429.0822; Found
429.0899.
Daidzein-4%,7-yl di-i- -glucopyranosiduro-
D
nic acid (4).—Complex 12 (2.34 mg, 2.64
mmol) was sonicated into suspension in
MeOH (300 mL) and stirred, and water (100
mL) and aq Na2CO3 (30 mL, 0.5 M, 15 mmol)
were added at 20 °C. After 90 min, further
MeOH (300 mL) and water (100 mL) were
added. After 150 min, all solids had dissolved.
The solution was desalted (Dowex 50W, H+)
and evaporated. Preparative HPLC gave 4;
1
purity was checked by analytical HPLC. H
NMR ((CD3)2SO): l 8.42 (s, 1 H, H-2), 8.03
(d, 1 H, J5,6 8.9 Hz, H-5), 7.50 (AA%BB% sys-
tem, 2 H, J2%,3% 8.4 Hz, H-2%, H-6%), 7.23 (d, 1
H, J8,6 2.4 Hz, H-8), 7.13 (dd, 1 H, H-6), 7.06
(AA%BB% system, 2 H, H-3%, H-5%), 5.10 (d, 1
H, J1,2 7.2 Hz, H-1%%), 4.92 (d, 1 H, J1,2 7.2 Hz,
H-1%%%), 4.01 (m, 2 H, H-5%% and H-5%%%), 3.3–3.7
(m, 6 H, H-2%%, H-2%%%, H-3%%, H-3%%%, H-4%% and
H-4%%%). ESMS: positive ion mode m/z 607
[M+H]+; negative ion mode m/z 605 [M−
H]−, 719 [M+TFA−H]−. FABMS (thio-
glycerol matrix): m/z [M−H]−. Anal. Calcd
605.1143; Found 605.1105.
Daidzein-4%,7-yl di-[methyl(2%%,3%%,4%%-tri-O-
acetyl-i- -glucopyranosiduronic acid)] (12).—
D
The trichloroimidate 8 (0.24 g, 0.50 mmol)
and daidzein 1 (62 mg, 0.24 mmol) were sus-
pended with stirring in CH2Cl2 (5 mL) at
−15 °C under Ar. BF3·Et2O (8 mL) was added
in one portion. The mixture was allowed to
warm to rt over 1 h, after which a further
portion of BF3·Et2O (8 mL) was added; stir-
ring was continued for 60 h. EtOAc (100 mL)
was added, and the mixture was washed with
satd NaHCO3 (2×50 mL), and water (1×50
mL), and dried (MgSO4). The solution was
evaporated to dryness, the resulting solid was
triturated with CH2Cl2, and the insoluble ma-
terial filtered off to yield recovered daidzein
(40 mg, 65%). The solution was evaporated,
and MPLC of the crude product, using 1%
MeOH–CH2Cl2 as eluant, gave 12, (29 mg,
Acknowledgements
This work was funded by the BBSRC. We
also wish to thank Dr Fred Mellon and Mr
John Eagles for performing mass spec-
troscopy, and Dr Ian Colquhoun for obtain-
ing the NMR data. We wish to acknowledge
the use of the EPSRC’s Chemical Database
Service at Daresbury.12
1
References
14%) as a colourless glass. H NMR (CDCl3):
8.24 (d, 1 H, J5,6 8.8 Hz, H-5), 7.94 (s, 1 H,
H-2), 7.49 (AA%BB% system, 2 H, J2%,3% 8.6 Hz,
H-2%, H-6%), 7.07 (AA%BB% system, 2 H, H-3%,
H-5%), 7.07 (d, 1 H, J8,6 2.4 Hz, H-8), 7.05 (dd,
1 H, H-6), 5.27-5.44 (m, 7 H, 1×H-1%% (7-sub-
stituent)), 2×H-2%%, 2×H-3%%, 2×H-4%%), 5.17
(d, 1 H, J1,2 6.8 Hz, H-1%% (4%-substituent)),
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