The synthesis and structure of the derivatives of 2-deoxy-2-hydroxyimino-D-lyxo-hexopyranosyl-L-cysteine and -thiophenol

Article abstract of DOI:10.1016/S0008-6215(00)00035-5

3,4,6-Tri-O-acetyl-2-deoxy-2-hydroxyimino-β and -α-D-lyxo-hexopyranosides of thiophenol (3, 4) and the methyl ester of N-benzoyl-L-cysteine have been synthesised by condensation of 3,4,6-tri-O-acetyl-2-deoxy-2-nitroso-α-D-galactopyranosyl chloride with thiophenol and the L-cysteine derivative, respectively. The conformation of the sugar residue and configuration of the anomeric centre as well as of the hydroxyimino group were established on the basis of the ¹H NMR (DQF-COSY, ROESY, TOCSY) spectrometric techniques and polarimetric data. Additionally, the structure of S-[3,4,6-tri-O-acetyl-2-deoxy-2-(Z)-hydroxyimino-β-D-lyxo-hexopyranosyl]-thiophenol (3) was supported by X-ray diffraction data. Copyright (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0008-6215(00)00035-5

www.elsevier.nl/locate/carres
Carbohydrate Research 326 (2000) 151–158
Note
The synthesis and structure of the derivatives of
2-deoxy-2-hydroxyimino-
D
-lyxo-hexopyranosyl- -cysteine
L
and -thiophenol
Beata Liberek a, Antoni Konitz a,b, Ryszard Frankowski a, Zygfryd Smiatacz a,*
a Faculty of Chemistry, Uni6ersity of Gdan´sk, Sobieskiego 18, PL-80-952 Gdan´sk, Poland
b Department of Inorganic Chemistry, Technical Uni6ersity of Gdan´sk, G. Narutowicza 11/12,
PL-80-952 Gdan´sk, Poland
Received 8 July 1999; accepted 16 January 2000
Abstract
3,4,6-Tri-O-acetyl-2-deoxy-2-hydroxyimino-b and -a-
ester of N-benzoyl- -cysteine have been synthesised by condensation of 3,4,6-tri-O-acetyl-2-deoxy-2-nitroso-a-
galactopyranosyl chloride with thiophenol and the -cysteine derivative, respectively. The conformation of the sugar
D
-lyxo-hexopyranosides of thiophenol (3, 4) and the methyl
L
D-
L
residue and configuration of the anomeric centre as well as of the hydroxyimino group were established on the basis
1
of the H NMR (DQF–COSY, ROESY, TOCSY) spectrometric techniques and polarimetric data. Additionally, the
structure of S-[3,4,6-tri-O-acetyl-2-deoxy-2-(Z)-hydroxyimino-b-
D
-lyxo-hexopyranosyl]-thiophenol (3) was sup-
ported by X-ray diffraction data. © 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Thioglycosides;
L
-Cysteine and thiophenol derivatives; 2-Deoxy-2-hydroxyimino sugars; Conformation and configura-
tion; X-ray diffraction
1. Introduction
age [8]. On the other hand, S-alkyl and S-aryl
glycosides are known as efficient donors of
Thioglycopeptides, which are rather rarely
found in nature, are conjugates of -cysteine
and -glucose or -galactose [1,2]. There is a
relatively small number of literature reports
concerned with the synthesis of these thiogly-
cosides [3–7], despite the fact that they may
play an important role in pharmacology be-
cause replacement of the anomeric oxygen of
O-glycopeptides by sulfur will change the
properties of the peptide–carbohydrate link-
glycosyls for glycosidation reactions [9]. The
phenylthioglycosides were successfully used
both as donors and acceptors of glycosyls in a
block synthesis of oligosaccharides [10].
L
D
D
Previously we have reported the synthesis of
some thioglycosides of
nol with the 2-deoxy-2-hydroxyimino-
L
-cysteine and thiophe-
-ara-
D
bino structure of the sugar residue [11], which
resulted in a variety of derivatives obtained by
chemical modification at C-2 and C-3. In the
present paper the same route was followed to
prepare thioglycosides of -cysteine and thio-
L
* Corresponding author. Tel.: +48-58-3450334.
E-mail address: smiatacz@chemik.chem.univ.gda.pl (Z.
Smiatacz)
phenol with the 2-deoxy-2-hydroxyimino- -
D
lyxo structure.
0008-6215/00/$ - see front matter © 2000 Elsevier Science Ltd. All rights reserved.
PII: S0008-6215(00)00035-5

152
B. Liberek et al. / Carbohydrate Research 326 (2000) 151–158
The a configuration of the anomeric car-
2. Results and discussion
bon atom was assigned for 4 and 5, and the
b configuration for 3 and 6. These findings
are supported by the [h]D values, which are
much lower for b anomers, and by analysis
The methyl ester of N,S-dibenzoyl- -cys-
L
teine (2) was methanolyzed just before reac-
tion with chloride 1. Under these conditions
only the benzoyl protection from the sulfur
atom was removed [12]. The reaction of
1
of H NMR spectra. Thus, the H-1 signal of
4 and 5 (6.60 and 6.52, respectively) appears
at higher l values than that of the analogous
proton of 3 and 6 (6.21 and 6.07, respec-
tively) owing to the respective equatorial and
axial orientation of H-1. The b configuration
of 3 and 6 was also demonstrated by the
investigation of the NOE effect in the
ROESY 1D experiment, where irradiation of
the H-1 proton caused the inversion of the
H-5, H-4, H-3, and OH signals (Fig. 1), as
expected for b anomers of this kind.
3,4,6-tri-O-acetyl-2-deoxy-2-nitroso-a- -galac-
D
topyranosyl chloride (1) with thiophenol
gave S-[3,4,6-tri-O-acetyl-2-deoxy-2-(Z)-hy-
droxyimino-b- (3) and a-
osyl]-thiophenol (4). Further, the reaction
of 1 with N-benzoyl- -cysteine methyl ester
D-lyxo-hexopyran-
L
afforded the methyl ester of N-benzoyl-S-
[3,4,6-tri-O-acetyl-2-deoxy-2-hydroxyimino-a-
(5) and -2-deoxy-2-(Z)-hydroxyimino-b- -
D
lyxo-hexopyranosyl]- -cysteine (6). The gly-
L
cosidation reaction was not stereospecific,
affording both the a and b anomers (a:bꢀ
2:1) with prevailing Z configuration of the
hydroxyimino group. Oxime 5 had a Z
Bearing in mind previous conclusions con-
cerning the influence of the 2-hydroxyimino
group on the position of signals of adjacent
protons [11,13], chemical shifts of H-1 and
H-3 in 3 (l 6.21 and 5.80, respectively), 4 (l
6.60 and 5.72, respectively), 5Z (l 6.52 and
5.72, respectively), 5E (l 5.94 and 5.85, re-
spectively) and 6 (6.07 and 5.80, respec-
tively), as well as the ROESY 1D
experiments for 3–6, it has been established
that the 2-hydroxyimino group has Z orien-
tation in 3, 4, 5Z and 6 and E orientation in
5E.
configuration in chloroform and
dimethyl sulfoxide.
E
in
1
Whilst recording the H NMR spectra in
chloroform, compound 5 with E configura-
tion of the hydroxyimino group underwent
transformation to isomer Z. This transfor-
mation (5E“5Z) did not take place in
dimethyl sulfoxide. As we previously re-
ported [11], the 5E“5Z transformation is
likely to be due to protonation of the nitro-
gen atom of the oxime group, which took
place in chloroform. Since the reverse trans-
formation (5Z“5E) did not occur either in
chloroform nor in dimethyl sulfoxide, we as-
sumed that isomer 5Z is thermodynamically
more stable than 5E.
The 2-hydroxyimino structure of com-
pounds 3–6 was established on the basis of
1
the H NMR spectra, namely by the struc-
ture of the H-1 (s) and H-3 (d) signals, by
intensity of the methyl signals corresponding
to three O-acetyl groups, and by the pres-
ence of a hydroxyl proton signal (s) at low
fields (lꢀ10–12). Further, the IR spectra of
these compounds exhibited bands due to the
OH (ꢀ3200 cm−1) and CꢀN (ꢀ1650
cm−1) vibrations.
Although the absence of the two useful
J1,2 and J2,3 proton coupling constants, as
well as
curate conformational deduction from 1H
NMR data, we propose that (Z)-a- -lyxo
compounds (4 and 5Z) with J3,4 3.42 and
D
-lyxo structure of 3–6, prevent ac-
D

B. Liberek et al. / Carbohydrate Research 326 (2000) 151–158
153
4
J4,5 ꢀ0 Hz have C1 conformation and (E)-a-
C1ꢁSPh, C2ꢀNꢁOH and C3ꢁOAc bonds (Fig.
2). These unfavourable interactions may cause
the adoption of any conformation other than
4C1 [15,16]. Taking into account our diffracto-
metric data for 3 and the fact that there is a
difference ꢀ0.4 ppm in the chemical shifts of
the H-1 signals of a and b anomers, indicative
of respective equatorial and axial orientation
of the H-1, we assumed the 3,OB conformation
for 3 and 6 in solution (Fig. 2). This is in
agreement with the ROESY 1D experiments
for 3 and 6. Interactions between H-1 and
H-5, H-4, H-3, respectively, demonstrated in
Fig. 1, were the strongest for H-1 and H-5,
while being the weakest for H-1 and H-3,
which is just possible in a 3,OB conformation.
D
-lyxo (5E) with J34,4 3.91 and J4,5 1.46 Hz
somewhat flattened C1 chair form. The cou-
pling constant J4,5 ꢀ1 Hz in the case of
D-
galactosides is in agreement with 4C1
4
conformation [14]. Deformation of the C1
chair form in 5E is due to the unfavourable
approach of the OH of oxime group at C-2
and the acetyl group at C-3. The examination
of key coupling constants of 3 (J3,4 4.39, J4,5
4.88 Hz) and 6 (J3,4 3.42, J4,5 5.86 Hz), both b
anomers with Z configuration of the hydroxy-
imino group, calls for a conformation other
4
than C1. This last form should be destabilised
owing to the strong electrostatic repulsion of
the nearly coplanar oriented dipoles of the
1
Fig. 1. H NMR spectra of the ROESY 1D type of 3.

154
B. Liberek et al. / Carbohydrate Research 326 (2000) 151–158
Fig. 2. Considered conformations for 3.
was performed on E. Merck Kieselgel 60 F254
Description of crystal structure.—In the
plates with: (A) 4:1:1 butanol–water–
CH3COOH; (B) 1:2 EtOAc–petroleum ether;
(C) 2:3 EtOAc–petroleum ether; (D) 3:1
crystal lattice, the compound shows two dif-
ferent conformations of the six-membered
pyranose ring (Fig. 3). The first molecule
1
adopts a C4 chair conformation with three
axial substituents (puckering parameters: q=
0.486 and ƒ=68.82°); the second molecule
shows a flattened boat conformation 3,OB with
only one axial substituent (puckering parame-
ters: q=0.687 and ƒ= −11.6°). Hydrogen-
bonded molecules of the same conformation
(O-2ꢁH···O-8 [x+1, y, z] and O-22ꢁH···O-28
[x−1, y−1, z]) form layers of parallel lines
perpendicular to the c axis with angles of
155.8 and 169.9° at the vertex hydrogen
atoms, respectively. Crystallographic data,
data collection and structure refinement are
presented in Table 1. Non-hydrogen atom co-
ordinates and equivalent isotropic tempera-
ture factors are presented in Table 2. Selected
bond lengths, valence angles and torsion an-
gles are given in Tables 3–5, respectively. The
values of bond lengths and angles determined
in this work agree well with the expected ones
[17].
3. Experimental
General methods.—Melting points are un-
corrected. Optical rotations were recorded us-
ing a Hilger–Watt polarimeter for solutions in
CHCl3. Thin-layer chromatography (TLC)
Fig. 3. Two independent molecules in the X-ray structure of
3.

B. Liberek et al. / Carbohydrate Research 326 (2000) 151–158
155
Table 1
Table 2
Atomic coordinates (×104) and equivalent isotropic displace-
Crystal data and summary of intensity and structure refine-
ment
2
3
a
,
ment parameters (A ×10 ) for 3
x
y
z
Ueq
59(1)
Compound
Colour/shape
3
colourless
prisms
C18H21NO8S
411.42
1296
S-1
N-1
O-1
O-2
O-3
O-4
O-5
O-6
O-7
O-8
C-1
C-2
C-3
C-4
C-5
C-6
1912(3)
5375(9)
1872(6)
5340(7)
3384(7)
4992(14)
2869(6)
5021(9)
6464(3)
3208(1)
3615(3)
4094(2)
3550(2)
3388(2)
3388(4)
4238(2)
4521(3)
3930(2)
3632(2)
3750(2)
3703(3)
3772(3)
4179(3)
4158(3)
3852(3)
3225(4)
2796(4)
4422(3)
4470(4)
3817(3)
3919(4)
3302(3)
3367(4)
3453(6)
3453(5)
3391(4)
3313(3)
1383(1)
2093(3)
1989(2)
2042(3)
1715(2)
1701(4)
2404(2)
2822(3)
2448(3)
2189(3)
1943(3)
2039(3)
2131(3)
2459(3)
2417(3)
2476(3)
1550(3)
1124(3)
2611(4)
2549(5)
2314(4)
2280(5)
1460(3)
1304(4)
1348(5)
1553(4)
1696(4)
1648(4)
8688(8)
7009(6)
7416(8)
10036(7)
12335(10)
10757(6)
12126(9)
6902(6)
62(2)
53(2)
70(2)
65(2)
163(6)
61(2)
92(2)
58(2)
63(2)
44(2)
49(2)
54(2)
49(2)
50(2)
48(2)
73(3)
105(5)
72(3)
100(4)
61(3)
79(3)
64(3)
90(4)
125(6)
131(7)
97(5)
66(3)
69(1)
78(3)
55(2)
101(3)
73(2)
130(4)
68(2)
106(3)
75(2)
90(2)
55(2)
55(2)
56(2)
61(3)
51(2)
60(2)
75(3)
90(4)
80(4)
104(4)
74(3)
97(4)
61(2)
90(4)
109(5)
95(4)
90(4)
74(3)
Empirical formula
Formula weight
F(000)
Space group
Cell constants
P32
,
a (A)
10.786(2)
10.786(2)
30.559(6)
120
3078.9(10)
6
,
b (A)
−723(6)
−1910(6)
2787(7)
,
c (A)
7892(7)
7069(8)
8494(9)
9809(9)
9585(8)
8216(8)
8264(8)
k (°)
3
,
Cell volume (A )
4135(9)
4060(9)
3159(8)
1683(8)
Formula units/unit cell
vcalc (mm−1
)
0.201
1.331
Dcalc (g cm−3
)
607(8)
Crystal size (mm)
Diffractometer
Radiation
Scan mode
Scan width
Standard reflections
Decay of standards
Reflections collected
Independent reflections
Reflections observed (F\2|(I))
2q Range (°)
0.3×0.3×0.6
Kuma KM4
Mo Ka
q/2q
1.4+tgq
331, 342, −224
14%
7264
4579
2197
1.8–54
C-7
C-8
C-9
4009(13)
3273(17)
3887(12)
3436(15)
−1900(10)
−3207(9)
873(10)
11358(11)
11370(17)
12003(10)
13069(10)
6875(10)
5526(11)
4593(9)
C-10
C-11
C-12
C-13
C-14
C-15
C-16
C-17
C-18
S-21
N-21
O-21
O-22
O-23
O-24
O-25
O-26
O-27
O-28
C-21
C-22
C-23
C-24
C-25
C-26
C-27
C-28
C-29
C-30
C-31
C-32
C-33
C-34
C-35
C-36
C-37
C-38
1592(13)
790(2)
3851(12)
2390(17)
1678(13)
2453(13)
3912(10)
7376(3)
4660(9)
8380(6)
4877(9)
6092(7)
−700(2)
−1390(11)
−601(9)
2697(3)
Ranges of h, k, l
−13“11,
0“13, 0“39
505
1921(10)
4710(6)
775(9)
5225(8)
4757(13)
6857(7)
6609(12)
6357(7)
8541(9)
3248(9)
3110(9)
No. of parameters varied
Function minimized
ꢀw(F2o−F2c)2
w
−1=|2(F2o)+(axP)2+bxP where
P=(Max(F2o, 0)+2F2c)/3
3833(11)
7364(7)
a
b
0.0827
0.0000
1.000
0.0774, 0.1657
0.1593, 0.2057
0.32
5558(10)
10836(7)
12145(8)
7266(8)
Goodness-of-fit
Rl, wR2 [I\2|(I)]
R1, wR2 (all reflections)
−3
,
Dzmax (e A
)
)
5844(8)
5835(8)
6968(9)
8291(8)
−3
,
Dzmin (e A
−0.33
4440(9)
5384(10)
5263(9)
6646(9)
9653(8)
5320(13)
6170(13)
7375(14)
8912(15)
7425(12)
7089(13)
1883(10)
503(13)
5005(13)
5374(15)
6593(12)
7237(16)
12069(11)
13211(12)
8437(10)
7899(14)
8739(15)
10068(15)
10596(12)
9795(10)
CCl4–acetone; (E) 1:1 toluene–EtOAc.
Column chromatography was performed on
MN Kieselgel 60 (B0.08 mm). The H NMR
1
spectra (CDCl3 or Me2SO, internal Me4Si)
were recorded with a Varian Unity Plus 500
(500 MHz) instrument. The IR spectra were
recorded as Nujol mulls with a Bruker IFS 66
spectrophotometer. Field desorption mass
spectra (FDMS) were recorded using a Varian
Mat 711 mass spectrometer. Elemental analy-
ses were conducted with a Carlo Erba EA1108
elemental analyser.
−122(14)
558(15)
1937(14)
2597(12)
a Ueq is defined as one third of the trace of the orthogonal-
ized Ujj tensor.

156
B. Liberek et al. / Carbohydrate Research 326 (2000) 151–158
Table 3
Molecular illustrations were drawn using the
ORTEP program [20].
,
Selected bond lengths (A) for 3
Dimeric
3,4,6-tri-O-acetyl-2-deoxy-2-ni-
1
Conformation C4
Conformation 3,OB
troso-h-D-galactopyranosyl chloride (1).—Pre-
pared according to the literature procedure
[21]; mp 128–130 °C, lit. 128–131 °C; [h]D20
+134° (c 0.5), lit. [h]2D3 +128° (c 2.2).
S-1ꢁC-1
N-1ꢁC-2
N-1ꢁO-2
O-1ꢁC-1
O-1ꢁC-5
O-3ꢁC-3
O-5ꢁC-4
C-1ꢁC-2
C-2ꢁC-3
C-3ꢁC-4
C-4ꢁC-5
C-5ꢁC-6
1.856(8)
1.276(10)
1.368(9)
1.421(9)
1.428(9)
1.465(9)
1.457(10)
1.504(10)
1.475(11)
1.523(11)
1.539(10)
1.512(10)
S-21ꢁC-21
N-21ꢁC-22
1.835(8)
1.291(10)
1.376(11)
1.433(9)
`
N-21ꢁO-22
0-21ꢁC-21
0-21ꢁC-25
0-23ꢁC-23
0-25ꢁC-24
C-21ꢁC-22
C-22ꢁC-23
C-23ꢁC-24
C-24ꢁC-25
C-25ꢁC-26
N,S-Dibenzoyl-
(2).—To a mixture of
L
-cysteine
methyl
-cysteine (2 g, 16.5
ester
1.460(9)
L
1.474(10)
1.435(10)
1.494(11)
1.466(12)
1.515(11)
1.503(11)
1.491(10)
mmol) and 1 M NaOH (50 mL, 50 mmol),
cooled to 0 °C, benzoyl chloride (4 mL) was
added with vigorous stirring, while the tem-
perature of the mixture was kept between 0
and 5 °C. The mixture was stirred for 30 min
at room temperature (rt). Neutralization of
the aqueous solution (ꢀ0 °C) with 36% HCl
Table 4
caused N,S-dibenzoyl- -cysteine to separate.
L
Selected valence angles (°) for 3
The precipitate was filtered off, washed with
cold water and dried. Recrystallisation from
1
Conformation C4
Conformation 3.OB
CHCl3 afforded pure N,S-dibenzoyl- -cys-
L
teine (50%); mp 173–175 °C; [h]2D0 −131° (c
0.49); Rf 0.84 (solvent A) (the structure was
C-2ꢁN-1ꢁO-2 111.4(8)
C-22ꢁN-21ꢁO-22 110.5(9)
C-1ꢁO-1ꢁC-5
O-1ꢁC-1ꢁC-2
O-1ꢁC-1ꢁS-1
C-2ꢁC-1ꢁS-1
118.2(6)
114.3(6)
115.1(5)
109.6(5)
C-21ꢁO-21ꢁC-25
O-21ꢁC-21ꢁC-22
O-21ꢁC-21ꢁS-21
C-22ꢁC-21ꢁS-21
110.4(6)
110.1(7)
107.1(5)
112.4(6)
1
confirmed by the H NMR and IR data).
Then a solution of N,S-dibenzoyl- -cysteine
L
(2.5 g, 7.6 mmol) in CH3OH saturated with
HCI (40 mL) was kept for 2 h in a refrigera-
tor. The precipitate was filtered off, washed
and dried to yield 2 (78%); mp 140–141 °C,
lit. 140–141 °C [12]; [h]2D0 +53° (c 0.48), lit.
[h]2D5 +55.5° (c 2) [12].
N-1ꢁC-2ꢁC-3 115.4(8)
N-1ꢁC-2ꢁC-1 125.9(8)
N-21ꢁC-22ꢁC-23 117.4(8)
N-21ꢁC-22ꢁC-21 125.5(9)
C-3ꢁC-2ꢁC-1
O-3ꢁC-3ꢁC-2
O-3ꢁC-3ꢁC-4
C-2ꢁC-3ꢁC-4
O-5ꢁC-4ꢁC-3
O-5ꢁC-4ꢁC-5
C-3ꢁC-4ꢁC-5
O-1ꢁC-5ꢁC-6
O-1ꢁC-5ꢁC-4
C-6ꢁC-5ꢁC-4
118.7(7)
108.6(7)
110.5(7)
107.5(7)
111.1(6)
105.6(6)
112.9(7)
114.0(7)
109.2(6)
115.9(7)
C-23ꢁC-22ꢁC-21
O-23ꢁC-23ꢁC-22
O-23ꢁC-23ꢁC-24
C-22ꢁC-23ꢁC-24
O-25ꢁC-24ꢁC-23
O-25ꢁC-24ꢁC-25
C-23ꢁC-24ꢁC-25
O-21ꢁC-25ꢁC-26
O-21ꢁC-25ꢁC-24
C-26ꢁC-25ꢁC-24
116.7(7)
107.9(7)
107.9(7)
112.7(7)
111.1(7)
108.4(7)
111.5(7)
106.6(6)
111.8(6)
114.0(7)
S-[3,4,6-Tri-O-acetyl-2-deoxy-2-(Z)-hydro-
xyimino-i- (3) and -h- -lyxo-hexopyranosyl]-
D
thiophenol (4).—A solution of 1 (0.675 g, 2
mmol) and thiophenol (0.41 mL, 4 mmol) in
DMF (20 mL) was stirred for 3 h at ꢀ20 °C
until the starting chloride 1 disappeared (TLC,
solvent B). Then the mixture was diluted with
CHCl3 (100 mL), washed with satd NaHCO3
solution (5×15 mL), water (5×15 mL), and
dried (Na2SO4). Concentration under dimin-
ished pressure gave a syrup, which was
chromatographed (solvent C) to afford first
3 (17%); mp 150–152 °C (CHCl3–n-heptane);
[h]2D0 −137° (c 0.48); Rf 0.37 (solvent C);
IR: w 3220 (OH), 1752 (ester CO), 1590
X-ray diffraction experiment.—X-ray mea-
surements were carried out on a KUMA KM-
4 four-circle diffractometer. The structures
were solved by direct methods with the
SHELXS program [18] and refined employing
the full-matrix least-squares method imple-
mented in the SHELXL program [19]. An-
isotropic displacement coefficients were
applied to all non-hydrogen atoms. All hydro-
gen atoms were refined in idealised positions
with isotropic temperature factors 1.2 times
the equivalent isotropic temperature factor of
the adjacent C or O atom. The atomic scatter-
ing factors were taken from the International
Tables for X-ray Crystallography (1993).
1
(CꢀN), 1226 (OꢁC) cm−1; H NMR (DMSO):
l 1.98, 2.09, 2.10 (3 s, 9 H, 3 AcO), 4.32
(dd, 1 H, J5,6% 4.89 Hz, H-6%), 4.40 (m, 1 H,
J5,6 8.54 Hz, H-5), 4.70 (dd, 1 H, J6,6%
11.48 Hz, H-6), 5.38 (t, 1 H, J4,5 4.88 Hz,
H-4), 5.80 (d, 1 H, J3,4 4.39 Hz, H-3), 6.21 (s,

B. Liberek et al. / Carbohydrate Research 326 (2000) 151–158
157
1 H, H-1), 7.40, 7.55 (2 m, 5 H, aromatic),
12.13 (s, 1 H, OH); FDMS: m/z 411 (M+).
Anal. Calcd for C18H21NO8S: C, 52.54; H,
5.15; N, 3.40; S, 7.79. Found: C, 52.32; H,
5.19; N, 3.42; S, 7.60.
was neutralised with AcOH and concentrated.
The crude residue was dissolved in DMF (10
mL) and added to the solution of 1 (0.545 g,
1.61 mmol) in DMF (10 mL). The resulting
solution was stirred at ꢀ20 °C until the start-
ing chloride 1 disappeared (3 h, TLC, solvent
D). Then the mixture was diluted with chloro-
form (100 mL), washed with satd NaHCO3
solution (5×15 mL), water (5×15 mL), and
dried (Na2SO4). Concentration under dimin-
ished pressure gave a syrup, which was chro-
matographed (solvent E) to yield first 5 (37%);
Eluted second was 4 (39%, syrup); [h]D20
+146° (c 0.51); Rf 0.29 (solvent C); IR: w 3200
(OH), 1745 (ester CO), 1650 (CꢀN), 1230
1
(OꢁC) cm−1; H NMR (DMSO): l 1.97, 2.03,
2.10 (3 s, 9 H, 3 AcO), 4.05 (d, 2 H, J5,6 6.35
Hz, 2 H-6), 4.85 (t, 1 H, H-5), 5.51 (d, 1 H,
J4,5 ꢀ0 Hz, H-4), 5.72 (d, 1 H, J3,4 3.42 Hz,
H-3), 6.60 (s, 1 H, H-1), 7.40, 7.55 (2 m, 5 H,
aromatic), 11.88 (s, 1 H, OH); FDMS: m/z
411 (M+). Anal. Calcd for C18H21NO8S: C,
52.54; H, 5.15; N, 3.40; S, 7.79. Found: C, 52.
14; H, 5.41; N, 3.04; S, 7.42.
mp 152–154 °C (CHCl3–n-heptane); [h]D20
+
98° (c 0.46); Rf 0.32 (solvent E); IR 3350
(OH), 1747 (ester CO), 1650 (amide I), 1536
1
(amide II), 1225 (OꢁC) cm−1; H NMR: 5Z
(CDCl3): l 1.96, 2.10, 2.17 (3 s, 9 H, 3 AcO),
3.34, 3.51 (2 dd, 2 H, CysꢁHb), 3.84 (s, 3 H,
CO2Me), 4.06 (dd, 1 H, J6,6% 11.23 Hz, H-6),
4.23 (dd, 1 H, J5,6% 5.37 Hz, H-6%), 4.68 (t, 1 H,
J5,6 7.33 Hz, H-5), 5.33 (m, 1 H, CysꢁHa), 5.51
(d, 1 H, J4,5ꢀ0 Hz, H-4), 5.72 (d, 1 H, J3,4
3.42 Hz, H-3), 6.52 (s, 1 H, H-1), 7.88 (d, 1H,
JNH, CH 7.57 Hz, CysꢁNH); 5E (DMSO): l
1.95, 2.00, 2.08 (3 s, 9 H, 3 AcO), 3.19 (m, 2
N-Benzoyl-S-[3,4,6-tri-O-acetyl-2-deoxy-2-
hydroxyimino-h- (5) and i-
anosyl]-
D
-lyxo-hexopyr-
L
-cysteine methyl ester (6).—To a sus-
pension of 2 (1.03 g, 3 mmol) in abs MeOH
(24 mL), 0.5 M methanolic CH3ONa (6 mL)
was added in an atmosphere of hydrogen with
stirring at ꢀ20 °C [12]. The ester dissolved
completely during 5 min, and then the mixture
Table 5
Selected torsion angles (°) for 3
1
Conformation C4
Conformation 3,OB
C-5ꢁO-1ꢁC-1ꢁC-2
C-5ꢁO-1ꢁC-1ꢁS-1
O-2ꢁN-1ꢁC-2ꢁC-3
O-2ꢁN-1ꢁC-2ꢁC-1
S-1ꢁC-1ꢁC-2ꢁN-1
O-1ꢁC-1ꢁC-2ꢁC-3
S-1ꢁC-1ꢁC-2ꢁC-3
N-1ꢁC-2ꢁC-3ꢁO-3
C-1ꢁC-2ꢁC-3ꢁO-3
C-1ꢁC-2ꢁC-3ꢁC-4
O-3ꢁC-3ꢁC-4ꢁO-5
C-2ꢁC-3ꢁC-4ꢁO-5
C-2ꢁC-3ꢁC-4ꢁC-5
O-3ꢁC-3ꢁC-4ꢁC-5
C-1ꢁO-1ꢁC-5ꢁC-6
C-1ꢁO-1ꢁC-5ꢁC-4
O-5ꢁC-4ꢁC-5ꢁO-1
C-3ꢁC-4ꢁC-5ꢁO-1
O-5ꢁC-4ꢁC-5ꢁC-6
C-3ꢁC-4ꢁC-5ꢁC-6
H-3ꢁC-3ꢁC-4ꢁH-4
H-4ꢁC-4ꢁC-5ꢁH-5
H-5ꢁC-5ꢁC-6ꢁH-6A
H-5ꢁC-5ꢁC-6ꢁH-6B
40.8(10)
−87.3(7)
−179.1(7)
2.0(12)
−88.4(9)
−38.1(10)
92.8(7)
105.8(8)
−75.2(9)
44.4(9)
−54.1(9)
−172.4(6)
−53.9(9)
64.4(9)
C-25ꢁO-21ꢁC-21ꢁC-22
C-25ꢁO-21ꢁC-21ꢁS-21
O-22ꢁN-21ꢁC-22ꢁC-23
O-22ꢁN-21ꢁC-22ꢁC-21
S-21ꢁC-21ꢁC-22ꢁN-21
O-21ꢁC-21ꢁC-22ꢁC-23
S-21ꢁC-21ꢁC-22ꢁC-23
N-21ꢁC-22ꢁC-23ꢁO-23
C-21ꢁC-22ꢁC-23ꢁO-23
C-21ꢁC-22ꢁC-23ꢁC-24
O-23ꢁC-23ꢁC-24ꢁO-25
C-22ꢁC-23ꢁC-24ꢁO-25
C-22ꢁC-23ꢁC-24ꢁC-25
O-23ꢁC-23ꢁC-24ꢁC-25
C-21ꢁO-21ꢁC-25ꢁC-26
C-21ꢁO-21ꢁC-25ꢁC-24
O-25ꢁC-24ꢁC-25ꢁO-21
C-23ꢁC-24ꢁC-25ꢁO-21
O-25ꢁC-24ꢁC-25ꢁC-26
C-23ꢁC-24ꢁC-25ꢁC-26
H-23ꢁC-23ꢁC-24ꢁH-24
H-24ꢁC-24ꢁC-25ꢁH-25
H-25ꢁC-25ꢁC-26ꢁH-26A
H-25ꢁC-25ꢁC-26ꢁH-26B
−53.0(9)
−175.6(5)
173.3(8)
1.0(13)
−72.0(11)
−3.7(10)
115.6(7)
114.3(9)
−72.6(9)
48.0(10)
−34.9(10)
−154.7(7)
−33.7(10)
86.1(9)
81.2(9)
−167.5(7)
67.3(9)
−50.4(9)
179.2(6)
57.5(9)
48.7(9)
−73.0(9)
−52.6
49.4
−177.5
61.3
102.1(8)
−20.4(10)
−18.9(10)
−141.4(8)
−35.4
−21.1
−177.3
63.2

158
B. Liberek et al. / Carbohydrate Research 326 (2000) 151–158
grants DS/8000-4-0026-9 and BW/8000-5-
H, CysꢁHb), 3.67 (s, 3 H, CO2Me), 4.07 (d, 2
H, 2 H-6), 4.63 (t, 1 H, J5,6 6.35 Hz, H-5), 4.71
(m, 1 H, CysꢁHa), 5.35 (dd, 1 H, J4,5 1.46 Hz,
H-4), 5.85 (d, 1 H, J3,4 3.91 Hz, H-3), 5.94 (s,
1 H, H-1), 8.92 (d, 1 H, JNH, CH 7.82 Hz,
CysꢁNH), 11.30 (s, 1 H, OH); FDMS: m/z
540 (M+). Anal. Calcd for C23H28N2O11S: C,
51.10; H, 5.22; N, 5.18; S, 5.93. Found: C,
50.80; H, 5.22; N, 5.03; S, 5.82.
0307-9.
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4. Supplementary material
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Acknowledgements
This research was supported by the Polish
State Committee for Scientific Research under
.
.