N-ACETYLMURAMYL-L-ALANYL-D-ISOGLUTAMINE GLYCOSIDES
291
acetate (Ic) (2.8 g, 6.5 mmol); yield 1.9 g (96%). An protecting group of the resulting glycopeptide (Vd)
analytical sample was crystallized from methanol; mp was removed by hydrolysis. The target compound
1
(VId) was isolated by precipitation with diethyl ether;
yield 290 mg (78%); amorphous substance; [α]546 +95°
(c 0.83, ethanol). For 1H NMR data, see table.
167–169°ë, [α]546 –37° (c 0.67, methanol). For H
NMR data, see table.
Cyclohexyl 2-acetamido-2-deoxy-4,6-O-isopropy-
lidene-β-D-glucopyranoside (IIIc) was synthesized by
isopropylidenation of triol (IIc) (830 mg, 2.74 mmol);
yield after column chromatography (elution with 75 : 1
O-(Heptyl 2-acetamido-2,3-dideoxy-α-D-glucopyr-
anosid-3-yl)-D-lactoyl-L-alanyl-D-isoglutamine (VIId)
was obtained by catalytic hydrogenolysis of benzyl
ester (VId) (190 mg, 0.29 mmol); yield 150 mg (90%);
amorphous powder; [α]546 +96° (c 0.67, ethanol).
benzene–ethanol
25 : 1 benzene–ethanol) 765 mg
(81%); glassy substance; [α]546 –69° (c 1.0, chloro-
form).
O-(Cyclohexyl 2-acetamido-2,3-dideoxy-a-D-glu-
copyranosid-3-yl)-D-lactoyl-L-alanyl-D-isoglutamine
(VIIe). Cyclohexyl 2-acetamido-2-deoxy-α-D-glucopy-
ranoside (IIe) was obtained by deacetylation of (Ic)
(3.43 g, 3.22 mmol); yield 2.42 g (100%). An analytical
sample was crystallized from methanol; mp 206–
207°ë, [α]546 +192° (c 1.0, ethanol). For 1H NMR data,
see table.
Cyclohexyl 2-acetamido-2-deoxy-4,6-O-isopropyl-
idene-α-D-glucopyranoside (IIIe) was synthesized by
isopropylidenation of triol (IIe) (1.0 g, 3.30 mmol); after
column chromatography (elution with benzene
20 : 1 benzene–ethanol), yield 925 mg (82%); amor-
phous powder; [α]546 +100° (c 1.0, chloroform).
Cyclohexyl-2-acetamido-2-deoxy-4,6-O-isopropyl-
idene-3-O-(D-1-carboxyethyl)-β-D-glucopyranoside
(IVc) was obtained by alkylation of acetal (IIIc)
(750 mg, 2.19 mmol) with (S)-bromopropionic acid;
yield 850 mg (94%); amorphous powder, [α]546 –6°
(c 1.0, chloroform).
O-Cyclohexyl 2-acetamido-2,3-dideoxy-β-D-glu-
copyranosid-3-yl)-D-lactoyl-L-alanyl-D-isoglutamine
benzyl ester (VIc). Muramic acid (IVc) (835 g,
2.01 mmol) was condensed with the dipeptide. The iso-
propylidene protecting group was removed from the
resulting compound (Vc) by hydrolysis. The target
compound (VIc) was isolated by column chromatogra-
phy (elution with chloroform
10 : 1 chloroform–
O-(Cyclohexyl 2-acetamido-2,3-dideoxy-α-D-glu-
copyranosid-3-yl)-D-lactoyl-L-alanyl-D-isoglutamine
benzyl ester (VIe). Acetal (IIIe) (910 mg, 2.65 mmol)
was alkylated with (S)-2-chloropropionic acid, and the
resulting muramic acid (IVe) was condensed with the
dipeptide. The isopropylidene protecting group of the
resulting compound (Ve) was removed by hydrolysis.
The target compound (VIe) was isolated by column
ethanol); yield 635 mg (48%); amorphous powder;
[α]546 +6° (Ò 1.0, ethanol). For 1H NMR data, see table.
O-(Cyclohexyl 2-acetamido-2,3-dideoxy-β-D-glu-
copyranosid-3-yl)-D-lactoyl-L-alanyl-D-isoglutamine
(VIIc) was obtained by catalytic hydrogenolysis of
benzyl ester (VIc) (325 mg, 0.49 mmol); yield 265 mg
(92%); amorphous powder; [α]546 +6° (Ò 0.67, ethanol).
O-(Heptyl
2-acetamido-2,3-dideoxy-a-D-glu-
chromatography (elution with chloroform
20 : 1
copyranosid-3-yl)-D-lactoyl-L-alanyl-D-isoglutamine
(VIId). Heptyl 2-acetamido-2-deoxy-α-D-glucopyra-
noside (IId) was obtained by deacetylation of acetate
(Id) (800 mg, 1.80 mmol); yield 500 mg (87%). An
analytical sample was crystallized from methanol; mp
163–165°ë, [α]546 +131° (Ò 1.0, methanol). For 1H NMR
data, see table.
chloroform–ethanol); yield 0.78 g (44%); amorphous
powder; [α]546 +98° (c 1.0, ethanol). For 1H NMR data,
see table.
O-(Cyclohexyl 2-acetamido-2,3-dideoxy-α-D-glu-
copyranosid-3-yl)-D-lactoyl-L-alanyl-D-isoglutamine
(VIIe) was obtained by catalytic hydrogenolysis of
benzyl ester (VIe) (380 mg, 0.57 mmol); yield 330 mg
(98%); amorphous powder; [α]546 +93° (c 1.0, ethanol).
Heptyl 2-acetamido-2-deoxy-4,6-O-isopropylidene-
α-D-glucopyranoside (IIId) was synthesized by iso-
propylidenation of triol (IId) (1.0 g, 3.30 mmol); after
column chromatography (elution with 75 : 1 benzene–
REFERENCES
ethanol
25 : 1 benzene–ethanol), yield 925 mg
1. Lefrancier, P., Derrien, M., Lederman, I., Nief, F.,
Choay, J., and Lederer, E., Int. J. Peptide Protein Res.,
1978, vol. 11, pp. 289–296.
(82%); glassy substance; [α]546 +100° (c 1.0, chloro-
form).
Heptyl 2-acetamido-2-deoxy-4,6-O-isopropylidene-
3-O-(D-1-carboxyethyl)-α-D-glucopyranoside (IVd)
was obtained by alkylation of acetal (IIId) (250 mg,
0.70 mmol) with (S)-2-chloropropionic acid; yield
228 mg (76%); amorphous powder, [α]546 +85° (c 1.0,
chloroform).
2. Durette, P.L., Dorn, C.P., Friedman, A., and Schla-
bach, A., J. Med. Chem., 1982, vol. 25, pp. 1028–1033.
3. Zemlyakov, A.E. and Chirva, V.Ya., Khim. Prir. Soedin.,
1987, no. 5, pp. 714–718.
4. Kur’yanov, V.O., Zemlyakov, A.E., and Chirva, V.Ya.,
Ukr. Khim. Zh., 1994, vol. 60, pp. 858–861.
O-Heptyl 2-acetamido-2,3-dideoxy-α-D-glucopyr-
anosid-3-yl)-D-lactoyl-L-alanyl-D-isoglutamine ben-
zyl ester (VId). Muramic acid (IVd) (228 g, 0.53 mmol)
was condensed with the dipeptide. The isopropylidene
5. Kur’yanov, V.O., Zemlyakov, A.E., and Chirva, V.Ya.,
Bioorg. Khim., 1994, vol. 20, pp. 439–447.
6. Kur’yanov, V.O., Zemlyakov, A.E., and Chirva, V.Ya.,
Bioorg. Khim., 1996, vol. 22, pp. 287–290.
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY Vol. 29 No. 3 2003