Synthesis of new amino sugar derivatives from keto-sugars of d-xylose

Article abstract of DOI:10.1016/j.carres.2006.06.018

Several amino sugars and imino sugar derivatives were synthesized from keto-sugars of d-xylose through a series of reactions such as the Henry reaction, hydrogenation reactions, and nucleophilic addition reactions or substitution reactions. Thiazine deriv

Full text of DOI:10.1016/j.carres.2006.06.018

Carbohydrate Research 341 (2006) 2312–2320
Synthesis of new amino sugar derivatives from
keto-sugars of D-xylose
Xiao-Ming Ji, Juan Mo, Hong-Min Liu* and He-Ping Sun
New Drug Research & Development Center, Zhengzhou University, Zhengzhou 450052, PR China
Received 11 April 2006; received in revised form 23 June 2006; accepted 26 June 2006
Available online 25 July 2006
Abstract—Several amino sugars and imino sugar derivatives were synthesized from keto-sugars of D-xylose through a series of reac-
tions such as the Henry reaction, hydrogenation reactions, and nucleophilic addition reactions or substitution reactions. Thiazine
derivative 15 was obtained by the reaction of the keto-sugar with NH2CSNH2. Higher carbon sugar 16 was accidentally prepared at
room temperature from the keto-sugar in the presence of NH2CONH2. The structures of the compounds were confirmed by spectral
analysis. The absolute configurations of all asymmetric carbon atoms of 6 and 8 were confirmed by X-ray crystallographic analysis.
ꢀ 2006 Elsevier Ltd. All rights reserved.
Keywords: Imino sugar; Amino sugar; Thiazine; Synthesis; X-ray crystallographic analysis
1. Introduction
sugars involved in these processes, a variety of monocy-
clic12 and bicyclic13 imino sugars have been synthesized
or isolated from natural sources over the years. Imino
sugar 1 was synthesized by reduction of a nitro com-
pound and acetylation;14 imino sugars 2 and 3 were
obtained by reduction of the corresponding cyano
compounds15 and imino sugar 410 and its homologues
were synthesized from other amino sugar precursors
(Fig. 1).
Compounds containing thiazine, thiazoline, or/and
thiazolidine rings have already been demonstrated to
be antitumor, analgesic, antibiotic, antiviral, antihista-
minic, anti-HIV, anti-inflammatory, and sedative
agents.16 Some thiazine derivatives were also proved to
have excellent NO synthase inhibition activities.17 The
development of simple and effective methods for their
preparation has aroused considerable interest in the field
of medicinal chemistry.
Carbohydrates and their derivatives are potentially use-
ful substrates in the chemical and biological fields. To
improve the function of compounds with new and
attractive characteristics,1 structural modifications can
occur by substitution with nitrogen, sulfur, phosphate,
or chlorine, and other groups.2 Amino sugars are very
important sugar derivatives, which are fundamental
constitutents3,4 of many biologically active compounds,
such as antibiotics5,6 and biopolymers.7 It is known, for
example, that the relative stereochemistry of the func-
tional groups in natural and unnatural amino sugars
plays an important role on the activity profile of the
anthracyclines.8 Especially heterocycles containing
nitrogen or sulfur (or both) are common features incor-
porated in the structures of numerous natural products
and pharmaceutical compounds.9 Some imino sugars
are glycosidase inhibitors with potential medicinal appli-
cations in the treatment of diabetes, obesity, and viral
infections including HIV-1.10 Due to their structural
resemblance to the putative transition states11 of the
O
O
H
HO
HO
O
AcN
AcO
OH
NH
NH
HN
OH
OH
O
Me
Me
OH
4
1
2
3
*
Corresponding author. Tel./fax: +86 371 67767200; e-mail: liuhm@
zzu.edu.cn
Figure 1. Examples of imino sugars.
0008-6215/$ - see front matter ꢀ 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2006.06.018

X.-M. Ji et al. / Carbohydrate Research 341 (2006) 2312–2320
2313
In this paper, several new branched-chain amino sugar
derivatives and some imino sugars bearing a pyrrole ring
similar to imino sugar 2 were synthesized from keto-
sugars derived from D-xylose. Thiazine derivative 15
was obtained by the reaction of the 3-keto-sugar with
NH2CSNH2, and a higher carbon sugar 16 was acciden-
tally obtained in the presence of NH2CONH2 at room
temperature from the 3-keto-sugar derivative of D-xylose.
by 1H, 13C, 2D NMR, and HRMS spectra, which
showed 7 and 8 to be isomers. The absolute structure
of 8 was confirmed by single-crystal X-ray analysis
(Fig. 2).
In order to control the yields of 7 and 8, the reaction
was investigated under various conditions. Prolonging
the reaction time and increasing the amount of the Pd/
C catalyst did not have an influence on the yields of 7
and 8. When a catalytic amount of concentrated hydro-
chloric acid was dropped to the reaction mixture, com-
pound 7 was obtained almost in quantitative yield, but
compound 8 was not observed. Product 7 could be
directly used in the subsequent reaction without prior
purification. It was found important to control the opti-
mum concentration range of hydrochloric acid between
0.10/100 (v/v) and 0.15/100 (v/v) to avoid the formation
of other products.
It is worth noting that when the catalytic hydrogena-
tion reaction was carried out in EtOH solution under
basic conditions, product 8 was obtained almost in
quantitative yield. The formation of 8 was deduced from
an intramolecular transfer of the benzoyl group in 7.18
In order to prove this process, amino sugar 7 was re-
fluxed in EtOH solution in the presence of Et3N, and
compound 8 was obtained in high yield.
Compound 8 is a useful precursor for the synthesis of
imino sugars. Sulfonylation of 8 with p-toluenesulfonyl
chloride in anhydrous pyridine at 0 ꢁC gave 9 in 90%
yield. Treatment of 9 with NaOMe in anhydrous THF
readily afforded a new imino sugar compound 10, which
is a bicyclic product containing a pyrrole ring. The
NMR spectra for 10 in dimethyl sulfoxide (DMSO-d6)
at room temperature suggested the presence of two iso-
mers. Such isomerism is due to restricted rotation about
the C–N bond.14
2. Results and discussion
2.1. Synthetic transformations
In the presence of KF, addition of nitromethane to the
carbonyl group of 5-O-benzoyl-1,2-O-isopropylidene-
a-D-erythro-ketofuranos-3-ulose (5), derived from D-
xylose, took place stereoselectively to give only the ribo
isomer 6 in almost quantitative yield (Scheme 1). KF
was found to be better than any other base for this reac-
tion. The presence of a nitro group in the structure was
indicated by IR spectral analysis, and the absolute con-
figuration of all asymmetric carbon atoms was con-
firmed by single-crystal X-ray crystallographic analysis
(Fig. 2). The stereoselectivity probably resulted from
the steric hindrance of the 1,2-O-isopropylidene group.
Reduction of the ribo isomer 6 with hydrogen over
10% palladium-on-charcoal under neutral conditions
led to a mixture of two products. The mixture was sep-
arated by silica gel column chromatography with 1:15
MeOH–CHCl3 to give the desired compound 7, 3-C-
aminomethyl-5-O-benzoyl-1,2-O-isopropylidene-a-D-ribo-
furanose, in 75% yield, plus an undesired compound 8,
3-C-benzamidomethyl-1,2-O-isopropylidene-a-D-ribofu-
ranose, in 10% yield. The structure of 8 was confirmed
BzO
O
NH2
HO
NHBz
O
b
c
d
+
O
O
O
Me
Me
Me
Me
O
HO
HO
BzO
BzO
7
8
O
O
NO2
a
7
O
O
TsO
O
O
NHBz
Me
Me
O
e
O
6
Me
Me
HO
5
O
Me
Me
O
HO
f
8
9
h
g
O
O
O
BzN
BzN
O
O
Me
Me
Me
10 Me
HO
HO
O
O
11
Scheme 1. Reagents and conditions: (a) KF, CH3NO2, THF, reflux; (b) EtOH, 10% Pd/C, 50 ꢁC, H2 (50 psi); (c) EtOH, HCl (aq), 10% Pd/C, 50 ꢁC,
H2 (50 psi); (d) EtOH, Et3N, 10% Pd/C, 50 ꢁC, H2 (50 psi); (e) EtOH, Et3N, reflux; (f) TsCl, pyridine, 0 ꢁC; (g) NaOMe, THF, reflux; (h) PDC,
CH2Cl2, reflux.

2314
X.-M. Ji et al. / Carbohydrate Research 341 (2006) 2312–2320
fonyl-a-D-ribofuranose (13), whose absolute structure is
that of a D-ribo sugar.14 Catalytic (10% Pd/C) hydro-
genation of compound 13 under neutral conditions for
2 h gave the desired imino sugar 14, which is a pyrrole
derivative. The reduction time (2 h) was shorter than
that for compound 6 (6 h), which should be a result of
p-toluenesulfonyl group elimination and imino sugar
formation.
Treatment of ulose 12 with thiourea in anhydrous
THF for 4 h at 40 ꢁC gave a new product 15 in 83%
yield. The HRMS of 15 exhibited molecular ions
[M+H]+ at m/z 247.0760 and [MꢀH]ꢀ at m/z 171.0110,
respectively, which showed 15 to be a p-toluenesulfonate
salt and also indicated the loss of the tosyl group from
1
C-5. The H NMR signals for H-5 shifted upfield by
Compound 6
0.86 and 0.77 ppm, respectively, whereas the 13C NMR
signals for C-5, appearing at d 24.3 ppm, large shifted
upfield by 33.7 ppm, in comparison with the spectra
for keto-sugar 12. Only the shifts of the SCH2 group
were in agreement with the above data.19 The HMBC
spectra indicated a long-distance coupling between
C@N and the C-5 proton. On the basis of the above
analysis and corresponding data, the structure of 15
was confirmed to be a sugar derivative containing a thi-
azine ring. It is shown that this reaction is a simple
method to obtain thiazine derivatives (Scheme 3).
In order to get access to other similar compounds,
treatment of ulose 12 with NH2CONH2 in anhydrous
THF at room temperature for 6 h accidentally led to a
higher carbon sugar 16 in 75% yield. The desired addi-
tion compound, similar to 15, was not observed. The
structure of compound 16 was confirmed from its
NMR and HRMS spectra. Under basic conditions,
higher carbon 16 was obtained through a hetero
Diels–Alder reaction,20 after the benzoyl group was
eliminated from the 5-position to form a diene. In a pre-
vious work, compound 16 was synthesized in the pres-
ence of KF at reflux temperature. The synthesis of 16
at room temperature was first reported in the presence
of NH2CONH2.
Compound 8
Figure 2. X-ray crystal structures of compounds 6 and 8.
Oxidation of 8 with pyridinium dichromate (PDC) at
reflux temperature (CH2Cl2) gave another bicyclic prod-
uct 11 containing a pyrrole ring in 81% yield. It was
likely that 8 was first oxidized to a carboxylic acid deriv-
ative, which was then transformed to lactam 11 by an
intramolecular cyclization as shown in Scheme 2.
Another derivative of D-xylose, 1,2-O-isopropylidene-
5-O-p-toluenesulfonyl-a-D-erythro-pentofuranos-3-ulose
(12), was treated with nitromethane at room tempera-
ture under basic conditions to give an addition product,
1,2-O-isopropylidene-3-C-nitromethyl-5-O-p-toluenesul-
Similarly, treatment of 12 with NH2NH2CSNH2, gave
an amithozone 17 in 80% yield; also no imino sugar was
obtained. Reduction of 17 with NaBH4 gave the par-
tially reduced product 18, another amino sugar contain-
ing a thio atom at the branch chain.
In summary, the synthesis of new branched amino
sugar derivatives, imino sugar derivatives with different
functional groups and C-10 higher carbon sugar from
O
HO
O
O
NHBz
O
HO C
O
O
–
H2O
PDC
BzN
O
Me
Me
C
O
N
O
O
O
Me
H
Me
Me
OH
O
HO
HO
Me
8
11
Scheme 2. A proposed mechanism for the formation of 11.

X.-M. Ji et al. / Carbohydrate Research 341 (2006) 2312–2320
2315
TsO
O
O
O
NO2
Me
b
a
HN
TsOH
O
O
OH
O
13
HO
Me
Me
Me
S
14
O
O
c
O
H N
TsOH
O
N
OH
2
Me
Me
TsO
O
Me
15
O
O
Me
Me
Me
O
O
O
12
O
O
d
O
Me
Me
O
16
O
TsO
O
TsO
S
O
e
f
HS
O
O
Me
Me
Me
Me
O
H2NHCHNN
O
H2NCHNN
17
18
Scheme 3. Reagents and conditions: (a) KF, CH3NO2, THF, rt; (b) EtOH, 10% Pd/C, 50 ꢁC, H2 (50 psi); (c) NH2CSNH2, THF, 40 ꢁC; (d)
NH2CONH2, rt, THF; (e) NH2NH2CSNH2, THF, rt; (f) NaBH4, MeOH, rt.
3-keto-D-erythro-pentofuranose is described. The struc-
The X-ray crystallographic analysis proved a D-ribo
configuration for compound 6. In compound 6, the fur-
an ring adopts the E conformation. The atoms of C(1),
C(2), C(3), and O(4) are coplanar. The plane equation is
ꢀ4.255x + 2.993y + 11.311z = 6.7983, while the C(4) is
1
tures of all products were confirmed by their IR, H
NMR, 13C NMR, and HRMS spectra. These com-
pounds could be useful in the chemical and medicinal–
chemical fields. Further studies on these sugars and their
derivatives are now in progress.
˚
away from the plane of 0.5354 A, and the flap atom
C(4) is placed in the exo direction. The substituted
dioxolane ring is in the E conformation. The atoms of
C(1), C(2), O(1), and O(2) are coplanar. The plane equa-
tion is 12.301x + ꢀ0.118y + ꢀ5.800z = 7.6908, while
2.2. X-ray crystallographic analysis
Details of the crystal structure determinations for com-
pounds 6 and 8 are summarized in Table 1. Selected tor-
sion angles are presented in Table 2.
˚
the C(7) is away from the plane of 0.4051 A and the flap
atom C(7) is placed in the exo direction. The sugar plane
Table 1. Single-crystal X-ray data and structure refinement for compounds 6 and 8
6
8
Empirical formula
Formula weight
Crystal system
Space group
C
353.32
Monoclinic
P21
16H19NO8
C16H21NO6
323.34
Orthorhombic
P212121
Unit cell dimensions
˚
a (A)
12.354
9.7016
˚
b (A)
5.501
13.514
12.821
13.439
˚
c (A)
Beta-angle
V (A )
110.28(3)
861.5(3)
90.00
1671.5(6)
3
˚
Z
2
4
DCalcd (Mg/m3)
1.362
0.110
372
1.285
0.099
688
Absorption coefficient (mmꢀ1
F(000)
Crystal size (mm3)
h Range for data collection (ꢁ)
Index ranges
Reflections collected/unique
Refinement method
Data/restrain/parameters
Final R indices [I > 2r(I)]
R Indices (all data)
Goodness-of-fit on F2
)
0.30 · 0.20 · 0.18
1.61–25.49
0 6 h 6 14, ꢀ5 6 k 6 6, ꢀ16 6 l 6 15
2175/2131 [R(int) = 0.1251]
Full-matrix least-squares on F2
2131/1/231
R1 = 0.0561, wR2 = 0.1224
R1 = 0.0704, wR2 = 0.1287
1.011
0.20 · 0.18 · 0.17
2.20–25.00
ꢀ11 6 h 6 11, 0 6 k 6 15, ꢀ15 6 l 6 15
5168/2761 [R(int) = 0.0264]
Full-matrix least-squares on F2
2761/0/221
R1 = 0.0330, wR2 = 0.0828
R1 = 0.0389, wR2 = 0.0849
1.032

2316
X.-M. Ji et al. / Carbohydrate Research 341 (2006) 2312–2320
Table 2. Selected torsion angles (ꢁ) for compounds 6 and 8
Compound 6 angle
Deg. (ꢁ)
Compound 8 angle
Deg. (ꢁ)
C(7)–O(1)–C(1)–C(2)
C(4)–O(4)–C(1)–O(1)
C(4)–O(4)–C(1)–C(2)
C(7)–O(2)–C(2)–C(3)
O(4)–C(1)–C(2)–O(2)
C(1)–C(2)–C(3)–C(4)
C(14)–C(15)–C(16)–C(11)
C(1)–O(1)–C(7)–O(2)
C(2)–O(2)–C(7)–O(1)
O(2)–C(2)–C(3)–C(4)
O(3)–C(3)–C(4)–C(5)
ꢀ10.3(4)
C(14)–O(1)–C(1)–C(2)
C(4)–O(3)–C(1)–O(1)
C(4)–O(3)–C(1)–C(2)
C(14)–O(2)–C(2)–C(3)
O(3)–C(1)–C(2)–O(2)
C(1)–C(2)–C(3)–C(4)
C(11)–C(12)–C(13)–C(8)
C(1)–O(1)–C(14)–O(2)
C(2)–O(2)–C(14)–O(1)
O(2)–C(2)–C(3)–C(4)
O(4)–C(3)–C(4)–C(5)
10.2(2)
107.70(16)
ꢀ6.82(19)
138.42(17)
94.93(16)
35.09(17)
ꢀ1.0(3)
94.0(4)
ꢀ19.5(4)
136.1(3)
108.5(3)
24.0(4)
ꢀ0.4(8)
25.2(4)
7.3(2)
ꢀ31.0(4)
ꢀ86.9(3)
80.8(5)
ꢀ23.2(2)
ꢀ73.98(16)
76.9(2)
and the substituted dioxolane plane fused along the
C(1)–C(2) bond allow the formation of a V-shaped
molecule with a 75ꢁ dihedral angle.
O(4)–H(4E)ꢁ ꢁ ꢁO(5), and O(5)–H(5E)ꢁ ꢁ ꢁO(6), respec-
tively, which results in a reticular molecular packing.
The hydrogen-bond lengths and bond angles for com-
pounds 6 and 8 are listed in Table 3.
The single-crystal X-ray diffraction analysis also re-
veals that there exists a kind of intermolecular hydrogen
bonding interaction between O(4) and H(3A) of O(3).
The neighboring molecules link to each other generating
a chain via the intermolecular hydrogen bonds. Finally,
the columns are bounded by the supramolecular interac-
tions among molecules to form a regular three-dimen-
sional network. The hydrogen-bond lengths and bond
angles are listed in Table 3.
3. Experimental
3.1. General procedures
Melting points were measured on a WC-1 melting-point
apparatus and are uncorrected. Infrared spectra were
recorded using KBr discs on a Bruker Vector-22 FTIR
spectrometer. Optical rotations were measured on a
Perkin–Elmer 341 polarimeter. HRMS (high-resolution
mass spectra) were taken with a Q-Tof Micromass
spectrometer. 1H NMR and 13C NMR spectra were
recorded on a Bruker Advance DPX-400 spectrometer
The X-ray crystallographic analysis proved a D-ribo
configuration for compound 8. Benzoyl group attach-
ment to the N atom is in agreement with the NMR spec-
tral analysis. In compound 8, the furan ring also adopts
the E conformation. Different from compound 6, the
atoms of C(1), C(2), C(4), and O(3) are coplanar in 8.
The plane equation is 6.849x + ꢀ1.643y + ꢀ9.361z =
2.9549, while the C(3) is away from the plane of
1
at 25 ꢁC. The H NMR and 13C NMR chemical shifts
(d), given in parts per million, were referenced to the
tetramethylsilane (TMS) signal. Coupling constants (J)
are given in hertz (Hz). Thin-layer chromatography
(TLC) was performed on glass plates precoated with
silica gel (5–40 lm, Qingdao Marine Chemical Factory
(China)) to monitor the reactions, and 10% Pd/C was
purchased from Shanghai Chemical Factory (China).
˚
0.6094 A and the flap atom C(3) is placed in the exo
direction. The substituted dioxolane ring adopts the E
conformation, and the atoms of C(1), C(14), O(1), and
O(2) are coplanar. The plane equation is 3.162x +
ꢀ2.306y + 12.473z = 6.1738, while the C(2) is away
˚
from the plane of ꢀ0.4059 A and the flap atom C(2) is
placed in the endo direction. The sugar plane and the
substituted dioxolane plane fused along the C(1)–C(2)
bond allow the formation of a V-shaped molecule with
a 66.8ꢁ dihedral angle.
3.2. X-ray diffraction experiment
X-ray diffraction analysis was carried out on a Rigaku
RAXIS-IV imaging plate with graphite monochro-
Different to 6, compound 8 makes contacts with three
neighboring molecules through N(1)–H(1E)ꢁ ꢁ ꢁO(1),
˚
mated Mo Ka radiation (k = 0.71073 A). An ortho-
Table 3. Hydrogen bonds for compounds 6 and 8
D–Hꢁ ꢁ ꢁA
6
d(D–H)
d(Hꢁ ꢁ ꢁA)
d(Dꢁ ꢁ ꢁA)
<(DHA)
165(6)
Symmetry code
O(3)–H(3A)ꢁ ꢁ ꢁO(4)
1.12(8)
1.72(8)
2.820(4)
x, y + 1, z
8
N(1)–H(1E)ꢁ ꢁ ꢁO(1)
O(4)–H(4E)ꢁ ꢁ ꢁO(5)
O(5)–H(5E)ꢁ ꢁ ꢁO(6)
0.90(2)
0.89(3)
0.85(3)
2.07(2)
1.93(3)
1.92(3)
2.948(2)
2.760(2)
2.732(2)
165.6(19)
155(3)
161(3)
ꢀx + 2, y ꢀ 1/2, ꢀz + 1/2
x ꢀ 1/2, ꢀy + 1/2, ꢀz + 1
ꢀx + 5/2, ꢀy + 1, z + 1/2

X.-M. Ji et al. / Carbohydrate Research 341 (2006) 2312–2320
2317
rhombic crystal and a monoclinic crystal were selected
and mounted on a glass fiber, respectively. All data
were collected at a temperature of 291(2) K and col-
lected for Lorentz polarization effects. The structure
was solved via direct methods and expanded using
the Fourier technique. The non-hydrogen atoms were
refined with anisotropic thermal parameters. Hydroxyl
hydrogen atoms were refined with isotropic thermal
parameters. Other hydrogen atoms were included but
not refined. All calculations were performed using the
SHELX-97 crystallographic software package.21 Atomic
coordinates and equivalent isotropic displacement
parameters for compounds 6 and 8 are presented in
Table 1.
affording compound 7 as a white solid (425 mg, 93%):
20
mp 163.2–164.4 ꢁC; ½aꢂD +16.5 (c 0.73, MeOH); Rf
0.40 (1:5 MeOH–CHCl3); IR (KBr): 3457, 2982, 1707,
1
1214, 1112, 1007 cmꢀ1; H NMR (DMSO-d6): d 1.29
(s, 3H, CH3), 1.51 (s, 3H, CH3), 2.92 (d, 1H, J6a,6b
13.2 Hz, H-6a), 3.01 (d, 1H, J6a,6b 13.2 Hz, H-6b), 4.22
(dd, 1H, J4,5b 3.0, J4,5a 6.9 Hz, H-4), 4.35 (dd, 1H,
J5a,4 7.0, J5a,5b 12.1 Hz, H-5a), 4.60 (dd, 1H, J4,5b 3.0,
J5a,5b 12.0 Hz, H-5b), 4.76 (d, 1H, J1,2 3.4 Hz, H-2),
5.81 (d, 1H, J1,2 3.6 Hz, H-1), 6.04 (s, 1H, OH-H),
7.54–7.99 (m, 5H, Ar–H), 8.25 (s, 2H, NH2–H); 13C
NMR (DMSO-d6): d 26.2 (CH3), 26.3 (CH3), 39.8 (C-
6), 61.5 (C-5), 77.2 (C-3), 77.7 (C-4), 78.9 (C-2), 102.9
(C-1), 111.6 (CH(CH3)2), 128.8 (Ar–C), 129.2 (Ar–C),
133.5 (Ar–C), 165.3 (C@O); HRMS: calcd for
[M+H]+: m/z 324.1447; found: m/z 324.1441.
(2) To a solution of compound 6 (500 mg, 1.42 mmol)
in EtOH (80 mL) was added 10% Pd/C (200 mg). The
mixture was hydrogenated at 50 ꢁC under 50 psi for
6 h. The resulting mixture was filtered and concentrated
under reduced pressure to dryness, and the crude prod-
uct was purified by chromatography on silica gel with
1:15 MeOH–CHCl3 to give 7 (345 mg, 75%) and 8
(46 mg, 10%), respectively.
3.3. 5-O-Benzoyl-1,2-O-isopropylidene-3-C-nitromethyl-
a-D-ribofuranose (6)
To a solution of compound 5 (500 mg, 1.71 mmol) in
anhyd THF (15 mL) was added CH3NO2 (2 mL,
37.1 mmol) and KF (125 mg, 2.1 mmol). The mixture
was refluxed for 50 min and evaporated in vacuum to
dryness. The residue was treated with EtOAc
(100 mL) and water (50 mL), the organic phase was
separated, and the aq phase was extracted with EtOAc
(2 · 50 mL). The combined organics were washed with
satd aq NaCl (2 · 15 mL), H2O (2 · 15 mL) dried over
anhyd Na2SO4. Filtration, evaporation, and crystalliza-
tion of the crude product from MeOH gave compound
6 as a white solid (575 mg, 95%): mp 159.5–161.0 ꢁC,
3.5. 3-C-Benzamidomethyl-1,2-O-isopropylidene-a-D-
ribofuranose (8)
(1) To a solution of compound 6 (500 mg, 1.42 mmol)
in EtOH (80 mL) was added 10% Pd/C (200 mg) and
Et3N (3 mL). The mixture was hydrogenated at 50 ꢁC
under 50 psi for 5 h. The resulting mixture was filtered
and concentrated under reduced pressure to dryness,
followed by crystallization from EtOH, affording com-
pound 8 as a white solid (413 mg, 91%): mp 189.1–
20
½aꢂD +12.3 (c 0.64, EtOAc); Rf 0.85 (7:3 CHCl3–
EtOAc); IR (KBr): 3397, 1726, 1553, 1281,
1007 cmꢀ1 1H NMR (CDCl3): d 1.41 (s, 3H, CH3),
;
1.62 (s, 3H, CH3), 4.26 (dd, 1H, J4,5b 4.4, J4,5a
6.0 Hz, H-4), 4.44 (dd, 1H, J4,5a 6.0, J5a,5b 12.0 Hz,
H-5a), 4.52 (d, 1H, J6a,6b 12.0 Hz, H-6a), 4.63 (dd,
1H, J4,5b 4.4, J5a,5b 12.0 Hz, H-5b), 4.81 (d, 1H, J6a,6b
12.0 Hz, H-6b), 4.91 (d, 1H, J2,1 4.0 Hz, H-2), 5.95
(d, 1H, J1,2 4.0 Hz, H-1), 7.44–8.05 (m, 5H, Ar–H);
13C NMR (CDCl3): d 26.2 (CH3), 26.5 (CH3), 60.5
(C-5), 76.2 (CH2NO2), 78.2 (C-3), 78.7 (C-4), 79.2 (C-
2), 103.5 (C-1), 113.4 (C(CH3)2), 128.5 (Ar–C), 129.1
(Ar–C), 129.7 (Ar–C), 133.4 (Ar–C), 165.9 (C@O);
HRMS: calcd for [M+Na]+: m/z 376.1008; found: m/z
376.1018.
20
190.2 ꢁC; ½aꢂD +55.0 (c 0.78, MeOH); Rf 0.60 (1:5
MeOH–CHCl3); IR (KBr): 3377, 3337, 1650, 1551,
1073, 1032 cmꢀ1 1H NMR (DMSO-d6): d 1.23 (s,
;
3H, CH3), 1.46 (s, 3H, CH3), 3.22 (dd, 1H, J6a,NH
5.3, J6a,6b 14.0 Hz, H-6a), 3.46 (dd, 1H, J6b,NH 6.9,
J6a,6b 13.9 Hz, H-6b), 3.56 (m, 1H, H-5), 3.63 (m, 1H,
H-5), 3.89 (dd, 1H, J4,5a 2.3, J4,5b 7.2 Hz, H-4), 4.26
(d, 1H, J2,1 3.7 Hz, H-2), 4.88 (t, 1H, J 5.4 Hz, OH-
5), 5.24 (s, 1H, OH-3), 5.70 (d, 1H, J1,2 3.7 Hz, H-1),
7.46–7.88 (m, 5H, Ar–H), 8.41 (t, 1H, J 6.0 Hz, NH);
13C NMR (DMSO-d6): d 26.6 (CH3), 26.9 (CH3),
41.4 (C-6), 59.0 (C-5), 79.8 (C-3), 80.8 (C-2), 82.1 (C-
4), 103.5 (C-1), 111.4 (C(CH3)2), 127.6 (Ar–C), 128.7
(Ar–C), 131.7 (Ar–C), 134.3 (Ar–C), 167.4 (C@O);
HRMS: calcd for [M+Na]+: m/z 346.1267; found:
m/z 346.1270.
3.4. 3-C-Aminomethyl-5-O-benzoyl-1,2-O-isopropylid-
ene-a-D-ribofuranose (7)
(1) To a solution of compound 6 (500 mg, 1.42 mmol) in
EtOH (80 mL) was added 10% Pd/C (200 mg) and
0.1 mL 37% aq HCl. The mixture was hydrogenated at
50 ꢁC under 50 psi for 5 h. The resulting mixture was
filtered and concentrated under reduced pressure to
dryness, followed by crystallization from EtOAc,
(2) To a solution of compound 7 (500 mg, 1.5 mmol)
in anhyd MeOH (10 mL) was added Et3N (0.5 mL).
The mixture was refluxed for 3 h, evaporated in vacuum,
and crystallized from EtOH to give compound 8 as a
white solid (412 mg, 90%).

2318
X.-M. Ji et al. / Carbohydrate Research 341 (2006) 2312–2320
3.6. 3-C-Benzamidomethyl-1,2-O-isopropylidene-5-O-p-
toluenesulfonyl-a-D-ribofuranose (9)
(Ar–C), 128.5 (Ar–C), 130.2 (Ar–C), 136.4 (Ar–C),
136.6 (Ar–C), 169.0 (C@O); HRMS: calcd for
[M+Na]+: m/z 328.1161; found: m/z 328.1165.
To a solution of compound 8 (500 mg, 1.5 mmol) in
anhyd pyridine (20 mL) was added p-toluenesulfonyl chlo-
ride (342 mg, 1.8 mmol) at 0 ꢁC. The mixture was stirred
for 24 h at 0 ꢁC, poured into 50 mL of ice-water, and ex-
tracted with EtOAc (2 · 50 mL). The combined organics
were washed with satd aq NaCl (2 · 15 mL), H2O
(2 · 15 mL), dried over anhyd Na2SO4, then filtered,
evaporated, and crystallized from MeOH to give com-
pound 9 as a white solid (665 mg, 90%): mp 144.6–
3.8. 3-C-Benzamidomethyl-1,2-O-isopropylidene-a-D-
ribofuranosonic acid 3,5-lactam (11)
To a solution of compound 8 (400 mg, 1.2 mmol) in
anhyd CH2Cl2 (20 mL) was added pyridinium dichromate
(PDC, 300 mg). The mixture was heated at reflux for
3 h, and then evaporated in vacuum. The residue was
dissolved in EtOAc and filtered through silica gel G.
The EtOAc layer was dried over Na2SO4, filtered, and
evaporated, and the crude product was crystallized from
MeOH to give compound 11 as a white solid (320 mg,
20
146.1 ꢁC; ½aꢂD +32.2 (c 0.53, EtOAc); Rf 0.7 (7:3
CHCl3–EtOAc); IR (KBr) 3449, 1647, 1530, 1362,
1173 cmꢀ1 1H NMR (CDCl3): d 1.31 (s, 3H, CH3),
;
20
1.53 (s, 3H, CH3), 2.45 (s, 3H, CH3), 3.32 (dd, 1H,
J6a,NH 4.4, J6a,6b 14.0 Hz, H-6a), 3.79 (dd, 1H, J6b,NH
8.0, J6a,6b 14.0 Hz, H-6b), 4.02 (dd, 1H, J4,5b 3.2, J4,5a
6.8 Hz, H-4), 4.14 (dd, 1H, J5a,4 6.8, J5a,5b 10.8 Hz, H-
5a), 4.29 (d, 1H, J2,1 3.6 Hz, H-2), 4.37 (dd, 1H, J5b,4
3.2, J5a,5b 10.8 Hz, H-5b), 5.81 (d, 1H, J1,2 4.0 Hz, H-
1), 6.66 (m, 1H, NHCO), 7.33–7.80 (m, 9H, Ar–H);
13C NMR (CDCl3): d 21.7 (CH3), 26.4 (CH3), 26.5
(CH3), 40.0 (C-6), 66.6 (C-5), 78.8 (C-4), 79.6 (C-3),
79.7 (C-2), 103.7 (C-1), 112.9 (CH(CH3)2), 127.0 (Ar–
C), 128.1 (Ar–C), 128.7 (Ar–C), 130.0 (Ar–C), 132.0
(Ar–C), 132.3 (Ar–C), 133.6 (Ar–C), 145.2 (Ar–C),
167.9 (C@O); HRMS: calcd for [M+Na]+: m/z
500.1355; found: m/z 500.1361.
81%): mp 162.5–165.4 ꢁC; ½aꢂD +155.6 (c 0.64, EtOAc);
Rf 0.6 (7:3 CHCl3–EtOAc); IR (KBr) 3455, 1763, 1676,
1321 cmꢀ1; 1H NMR (CDCl3): d 1.44 (s, 3H, CH3), 1.63
(s, 3H, CH3), 3.92 (d, 1H, J6a,6b 12.8 Hz, H-6a), 4.19 (d,
1H, J6a,6b 12.8 Hz, H-6b), 4.37 (s, 1H, H-4), 4.53 (d, 1H,
J1,2 3.7 Hz, H-2), 6.06 (d, 1H, J1,2 3.7 Hz, H-1), 7.43–
7.65 (m, 5H, Ar–H); 13C NMR (CDCl3): d 26.9 (CH3),
27.1 (CH3), 53.6 (C-6), 78.8 (C-3), 81.5 (C-4), 84.7 (C-
2), 107.1 (C-1), 114.5 (CH(CH3)2), 128.0 (Ar–C), 129.1
(Ar–C), 132.5 (Ar–C), 133.4 (Ar–C), 167.8 (C@O),
170.3 (C@O); HRMS: calcd for [M+Na+MeOH]+:
m/z 374.1216; found: m/z 374.1212.
3.9. 1,2-O-Isopropylidene-3-C-nitromethyl-5-O-p-tolu-
enesulfonyl-a-D-ribofuranose (13)
3.7. N-Benzoyl-5-deoxy-3,5-imino-1,2-O-isopropylidene-
a-D-ribofuranose (10)
To a solution of compound 12 (500 mg, 1.46 mmol) in
anhyd THF (15 mL) was added CH3NO2 (2 mL,
37.1 mmol) and KF (125 mg, 2.1 mmol). The mixture
was stirred at room temperature for 6 h and then evap-
orated in vacuum to dryness. The residue was treated
with EtOAc (100 mL) and water (50 mL), the organic
phase was separated, and the aq phase was extracted
with EtOAc (2 · 50 mL). The combined organics were
dried over anhyd Na2SO4, filtered, evaporated, and crys-
tallized from MeOH to afford compound 13 as a white
solid (536 mg, 91%): mp 133.0–134.0 ꢁC, lit.14 131.5–
To a solution of compound 9 (500 mg, 1.04 mmol) in
anhyd THF (20 mL) was added NaOMe (0.5 mL). The
mixture was refluxed for 5 h, and then evaporated in
vacuum. The residue was dissolved in water, extracted
with EtOAc, and the organic layer was dried over
Na2SO4, and then filtered, evaporated, and crystallized
from MeOH to give compound 10 as a white solid
20
(273 mg, 86%): mp 203.2–203.8 ꢁC; ½aꢂD +145.7 (c
0.74, CHCl3); Rf 0.4 (7:3 CHCl3–EtOAc); IR (KBr)
20
3170, 1606, 1593, 1572, 1459, 1438, 1067 cmꢀ1
;
1H
132 ꢁC; ½aꢂD +23.7 (c 0.65, EtOAc); Rf 0.85 (7:3
NMR (DMSO-d6): d 1.26 (s, 3H, CH3), 1.28 (s, 3H,
CH3), 1.47 (s, 3H, CH3), 1.48 (s, 3H, CH3), 3.34 (m,
1H, H-6), 3.43 (d, 1H, J 12.4 Hz, H-5), 3.53 (d, 3H, J
12.4 Hz, H-6), 3.65 (t, 1H, J 13.8 Hz, H-5), 3.73 (m,
2H, H-5), 4.23 (d, 1H, J 2.9 Hz, H-4), 4.32 (d, 1H, J
3.4 Hz, H-4), 4.38 (d, 1H, J 3.6 Hz, H-2), 4.54 (d, 1H,
J 3.6 Hz, H-2), 5.58 (s, 1H, OH-3), 5.63 (s, 1H, OH-3),
5.84 (d, 1H, J 3.6 Hz, H-1), 5.86 (d, 1H, J 3.6 Hz, H-
1), 7.42–7.51 (m, 10H, Ar–H); 13C NMR (DMSO-d6):
d 26.7 (CH3), 27.0 (CH3), 50.3 (C-5), 52.9 (C-5), 55.1
(C-6), 57.2 (C-6), 80.1 (C-2), 80.7 (C-2), 81.2 (C-4),
82.6 (C-4), 83.9 (C-3), 85.7 (C-3), 105.2 (C-1), 111.9
(CH(CH3)2), 112.0 (CH(CH3)2), 127.3 (Ar–C), 128.5
CHCl3–EtOAc); IR (KBr): 3462, 1555, 1364, 1174,
1101, 992 cmꢀ1 1H NMR (CDCl3): d 1.38 (s, 3H,
;
CH3), 1.56 (s, 3H, CH3), 2.46 (s, 3H, CH3), 4.06 (t,
1H, J4,5a 4.0 Hz, H-4), 4.18 (dd, 1H, J5a,4 4.8, J5a,5b
11.2 Hz, H-5a), 4.30 (dd, 1H, J5a,5b 11.2, J5b,4 3.2 Hz,
H-5b), 4.40 (d, 1H, J6a,6b 12.0 Hz, H-6a), 4.62 (d, 1H,
J6a,6b 12.0 Hz, H-6b), 4.82 (d, 1H, J2,1 4.0 Hz, H-2),
5.85 (d, 1H, J1,2 4.0 Hz, H-1), 7.36–7.81 (m, 4H, Ar–
H); 13C NMR (CDCl3): d 21.7 (CH3), 26.2 (CH3), 26.5
(CH3), 65.3 (C-5), 76.3 (C-6), 78.0 (C-3), 78.9 (C-4),
79.3 (C-2), 103.5 (C-1), 113.6 (C(CH3)2), 128.1 (Ar–C),
130.1 (Ar–C), 132.1 (Ar–C), 145.5 (Ar–C); HRMS:
calcd for [M+Na]+: m/z 426.0835; found: m/z

X.-M. Ji et al. / Carbohydrate Research 341 (2006) 2312–2320
2319
426.0822; calcd for [M+K]+: m/z 442.0574; found: m/z
442.0569.
1.60 mmol). The mixture was stirred at room tempera-
ture for 6 h and evaporated to dryness. The residue
was dissolved in water (50 mL), extracted with EtOAc
(2 · 50 mL), and the combined organics were dried over
anhyd Na2SO4, filtered, and evaporated. The crude
product was crystallized from Et2O to afford compound
16 as a white solid (371 mg, 75%): mp 166.1–168.0 ꢁC;
3.10. 5-Deoxy-3,5-imino-1,2-O-isopropylidene-a-D-ribo-
furanose, p-toluenesulfonate salt (14)
To a solution of compound 13 (500 mg, 1.2 mmol) in
MeOH (80 mL) was added 10% Pd/C (200 mg). The
mixture was hydrogenated at 50 ꢁC under 50 psi for
2 h. The resulting mixture was filtered and concentrated
under reduced pressure to dryness, followed by crystal-
lization from MeOH, affording compound 14 as a white
20
½aꢂD +49.1 (c 0.20, CHCl3); Rf 0.60 (7:3 CHCl3–EtOAc);
1
IR (KBr): 3440, 2990, 1794, 1634, 1214, 1090 cmꢀ1; H
NMR (DMSO-d6): d 1.35 (s, 3H, CH3), 1.38 (s, 3H,
CH3), 1.41 (s, 3H, CH3), 1.43 (s, 3H, CH3), 1.93 (m,
1H, H-5a), 2.03 (m, 1H, H-5b), 2.27 (m, 1H, H-6a),
2.34 (m, 1H, H-6b), 5.10 (d, 1H, J1,2 4.4 Hz, H-2),
5.22 (d, 1H, J9,10 5.2 Hz, H-9), 5.99 (d, 1H, J10,9
5.2 Hz, H-10), 6.10 (d, 1H, J1,2 4.4 Hz, H-1), 13C
NMR (DMSO-d6): d 17.1 (C-6), 25.4 (C-5), 27.1
(CH3), 27.4 (CH3), 27.5 (CH3), 27.9 (CH3), 76.0 (C-2),
79.9 (C-9), 99.9 (C-4), 101.9 (C-1), 103.6 (C-10), 112.1
(C-11), 115.4 (C-14), 129.6 (C-8), 137.3 (C-7), 202.5
(C-3); HRMS: calcd for [M+Na+MeOH]+: m/z
395.1318; found: m/z 395.1321.
20
solid (415 mg, 89%): mp 190.7–192.8 ꢁC; ½aꢂD +36.3 (c
0.73, MeOH); Rf 0.40 (1:3 MeOH–CHCl3); IR (KBr):
3367, 2979, 1617, 1195, 1175, 1081, 1011 cmꢀ1 1H
;
NMR (DMSO-d6): d 1.29 (s, 3H, CH3), 1.49 (s, 3H,
CH3), 2.29 (s, 3H, CH3), 3.34 (m, 2H, H-6), 3.38 (m,
2H, H-5), 4.38 (d, 1H, J4,5 2.8 Hz, H-4), 4.56 (d, 1H,
J2,1 3.6 Hz, H-2), 5.85 (d, 1H, J1,2 3.6 Hz, H-1), 5.97
(s, 1H, OH-3), 7.11–7.50 (m, 4H, Ar–H), 9.30 (s, 1H,
COOH); 13C NMR (DMSO-d6): d 21.0 (CH3), 26.7
(CH3), 26.9 (CH3), 49.1 (C-5), 52.8 (C-6), 80.0 (C-2),
82.6 (C-4), 86.3 (C-3), 105.2 (C-1), 112.4 (C(CH3)2),
125.7 (Ar–C), 128.3 (Ar–C), 137.9 (Ar–C), 145.7 (Ar–
C); HRMS: calcd for [M+H]+: m/z 202.1079; found:
m/z 202.1079; calcd for [MꢀH]ꢀ: m/z 171.0116; found:
m/z 171.0119.
3.13. 1,2-O-Isopropylidene-5-O-p-toluenesulfonyl-a-D-
erythro-ketofuranose-3-ulose 3-thiosemicarbazone (17)
To a solution of compound 12 (500 mg, 1.46 mmol) in
THF (20 mL) was added NH2NH2CSNH2 (145 mg,
1.60 mmol). The mixture was stirred at room tempera-
ture for 5 h, and evaporated to dryness. The residue
was treated with EtOAc (100 mL) and water (50 mL),
the organic phase was separated, and the aq phase was
extracted with EtOAc (2 · 50 mL). The combined
organics were dried over anhyd Na2SO4, filtered, and
evaporated. The residue was purified by chromatogra-
phy (9:1 CHCl3–EtOAc) to give compound 17 as a syrup
3.11. (3aR,4aS,8aS,8bR)-7-amino-2,2-dimethyl-3a,4a,
5,8b-tetrahydro-8aH-[1,3]dioxolo[4,5]furo[3,2-d][1,3]thi-
azin-8a-ol (15)
To a solution of compound 12 (500 mg, 1.46 mmol) in
THF (20 mL) was added NH2CSNH2 (122 mg,
1.60 mmol). The mixture was heated at 40 ꢁC for 4 h,
then evaporated to dryness. The crude product was crys-
tallized from EtOAc to give compound 15 as a white
20
(511 mg, 80%): ½aꢂD +220.0 (c 0.75, CHCl3); Rf 0.6 (1:1
EtOAc–petroleum ether); IR (KBr): 3338, 1598, 1494,
20
1
solid (350 mg, 83%): mp 190.5–191.6 ꢁC; ½aꢂD ꢀ64.9 (c 1.0,
1359, 1176, 1065 cmꢀ1; H NMR (CDCl3): d 1.42 (s,
MeOH); Rf 0.40 (1:5 MeOH–CHCl3); IR (KBr): 3303,
6H, 2CH3), 2.47 (s, 3H, CH3), 4.25 (dd, 1H, J5a,4 2.6,
J5a,5b 10.8 Hz, H-5a), 4.31 (dd, 1H, J5b,4 2.4, J5a,5b
10.8 Hz, H-5b), 4.86 (m, 1H, H-4), 5.00 (d, 1H, J1,2
4.6 Hz, H-2), 5.96 (d, 1H, J1,2 4.6 Hz, H-1), 6.49 (s,
1H, NH2), 7.10 (s, 1H, NH2), 7.27–7.75 (m, 4H, Ar–
H), 9.20 (s, 1H, NH); 13C NMR (CDCl3): d 21.7
(CH3), 27.2 (CH3), 27.4 (CH3), 69.3 (C-5), 74.2 (C-2),
76.8 (C-4), 104.8 (C-1), 114.6 (C(CH3)2), 127.8 (Ar–C),
130.1 (Ar–C), 132.4 (Ar–C), 145.5 (Ar–C), 150.3 (C-3),
179.6 (C@S); HRMS: calcd for [M+Na]+: m/z
438.0769; found: m/z 438.0758.
1
1654, 1614, 1486, 1216, 1090 cmꢀ1; H NMR (D2O): d
1.34 (s, 3H, CH3), 1.54 (s, 3H, CH3), 2.33 (s, 3H,
CH3), 3.40 (dd, 1H, J5a,4 3.9, J5a,5b 14.6 Hz, H-5a),
3.52 (d, 1H, J5a,5b 14.6 Hz, H-5b), 4.52 (m, 1H, H-4),
4.60 (d, 1H, J2,1 3.6 Hz, H-2), 5.88 (d, 1H, J2,1 3.6 Hz,
H-1), 7.30–7.63 (m, 4H, Ar–H); 13C NMR (D2O): d
20.9 (CH3), 24.3 (C-5), 25.9 (CH3), 26.0 (CH3), 70.0
(C-4), 82.2 (C-2), 86.1 (C-3), 104.0 (C-1), 115.4
(C(CH3)2), 125.8 (Ar–C), 129.9 (Ar–C), 139.9 (Ar–C),
142.9 (Ar–C), 168.0 (C@N); HRMS: calcd for
[M+H]+: 247.0753; found: 247.0760; calcd for [MꢀH]ꢀ:
171.0116; found: 171.0110.
3.14. 1,2-O-Isopropylidene-5-O-p-toluenesulfonyl-a-D-
erythro-ketofuranose-3-ulose 3-hydrothiosemicarbazone
(18)
3.12. Carbon-10 higher carbon compound (16)
To a solution of compound 12 (500 mg, 1.46 mmol) in
To a solution of compound 17 (500 mg, 1.20 mmol) in
THF (20 mL) was added NH2CONH2 (96 mg,
anhyd MeOH (20 mL) was added NaBH4 (70 mg,

2320
X.-M. Ji et al. / Carbohydrate Research 341 (2006) 2312–2320
1.81 mmol). The mixture was stirred at room tempera-
ture for 5 h, and then concentrated. The crude product
was submitted to silica gel column chromatography
(1:1 CHCl3–EtOAc) to afford compound 18 as a white
tronic version of this paper and can be accessed at
doi:10.1016/j.carres.2006.06.018.
References
20
solid (392 mg, 78%): mp 125.0–126.1 ꢁC, ½aꢂD +96.6 (c
0.45, CHCl3); Rf 0.6 (7:3 CHCl3–EtOAc); IR (KBr):
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3346, 1596, 1360, 1190, 1175 cmꢀ1; H NMR (CDCl3):
d 1.36 (s, 3H, CH3), 1.52 (s, 3H, CH3), 2.46 (s, 3H,
CH3), 3.39 (dd, 1H, J 4.0 Hz, H-CHS), 3.89 (m, 1H,
H-4), 4.22 (dd, 1H, J5a,4 2.7, J5a,5b 11.2 Hz, H-5a),
4.32 (dd, 1H, J5b,4 3.1, J5a,5b 11.3 Hz, H-5b), 4.50 (s,
1H, SH) 4.74 (t, 1H, J1,2 3.6 Hz, H-2), 5.77 (d, 1H,
J1,2 3.6 Hz, H-1), 6.45 (s, 1H, NH2), 7.24 (s, 1H,
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(CH3), 63.0 (C-S), 67.5 (C-5), 75.0 (C-4), 77.2 (C-2),
104.6 (C-1), 113.1 (C(CH3)2), 128.0 (Ar–C), 130.1
(Ar–C), 130.1 (C-3), 132.3 (Ar–C), 145.5 (Ar–C);
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Acknowledgment
We are grateful to NNSF of PR China (NO. 20472075)
for financial support of this work.
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