An efficient and convenient formal synthesis of Jaspine B from d-xylose

Article abstract of DOI:10.1016/j.carres.2012.01.013

A formal synthesis of Jaspine B was completed in 42.4% overall yield with only three purification steps (one by crystallization and two by column chromatography). The key step in the synthesis involves a regio- and stereoselective epoxide ring-opening reaction and the configuration inversion of the C3-hydroxyl group through oxidation and reduction. All of the reagents and materials used were quite common and inexpensive.

Full text of DOI:10.1016/j.carres.2012.01.013

Carbohydrate Research 351 (2012) 126–129
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Carbohydrate Research
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Note
An efficient and convenient formal synthesis of Jaspine B from D-xylose
⇑
Ming-Li Zhao, En Zhang, Jie Gao, Zhao Zhang, Yu-Tao Zhao, Wen Qu, Hong-Min Liu
School of Pharmaceutical Sciences, Zhengzhou University, Zhengzhou 450001, PR China
New Drug Research and Development Center, Zhengzhou University, Zhengzhou 450001, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A formal synthesis of Jaspine B was completed in 42.4% overall yield with only three purification steps
(one by crystallization and two by column chromatography). The key step in the synthesis involves a
regio- and stereoselective epoxide ring-opening reaction and the configuration inversion of the C3-
hydroxyl group through oxidation and reduction. All of the reagents and materials used were quite com-
mon and inexpensive.
Received 22 December 2011
Received in revised form 14 January 2012
Accepted 19 January 2012
Available online 28 January 2012
Ó 2012 Elsevier Ltd. All rights reserved.
Keywords:
Jaspine B
D-Xylose
Formal synthesis
Jaspine B (1), also known as pachastrissamine, is a naturally
occurring novel anhydrosphingosine derivative, which was iso-
lated by Higa and co-workers in 2002 from the Okinawa marine
sponge Pachastrissa sp. (family Calthropellidae) and was found to
C3-hydroxy; group. Alcohol 4 can be derived from an epoxide 5
via a regio- and stereoselective epoxide ring-opening reaction as
reported by Wightman.17 The epoxide 5 can be easily prepared
from
First, D-xylose was treated with concentrated H2SO4 in acetone
D
-xylose.18
possess cytotoxicity at an IC50 level of 0.01
lg/mL against P388,
A549, HT29, and Mell 28 cell lines.1 Shortly thereafter, Debitus
and co-workers reported the isolation of the same natural product
from a different marine sponge Jaspis sp.2
to give 1,2-acetal 7 in a 88% yield19 (Scheme 2). Tosylation of 7
with tosyl chloride and pyridine in CH2Cl2 at room temperature
afforded 6, which could be crystallized in a 82% yield. Acid-cata-
lyzed furan ring formation and epoxide generation led to 5 in a
94% yield. The 1,2-azido alcohol 4 was formed via ring-opening
reaction of epoxide 5 with NaN3 in a 95% yield.
Due to its impressive biological activity, novel structural fea-
tures, and the lack of structure–activity relationship (SAR) studies
on Jaspine B, much effort has been devoted to research of this
interesting natural product.3–6 However, SAR of this molecule is
still scarce, which has prompted extensive synthetic studies of
Jaspine B and its analogues.7–12
Then the main problem was the configuration change of the C3-
hydroxyl group of 1,2-azido alcohol 4. Oxidation and stereoselec-
tive reduction were used due to steric hindrance. Thus, oxidation
of 1,2-azido alcohol 4 followed by stereoselective reduction fur-
nished a mixture of diastereomeric alcohols 3 and 4. Reaction of this
mixture of alcohols with benzyl bromide in the presence of potas-
sium carbonate resulted in 2 and 20 (Table 1), which could be sepa-
rated easily via column chromatography due to a huge difference of
Rf value. Compound 20 would be of use for preparing 3-epi Jaspine B.
The influence of reaction conditions of oxidation and reduction
were examined as summarized in Table 1. When IBX was used as
the oxidant, an excellent yield was observed (entry 4). Swern oxi-
dation and PDC oxidation could also be used, and lower yields were
observed (entries 1 and 2). However, no product was obtained by
employing DMSO and acetic anhydride (entry 3). Thus, IBX was
the best choice for the reaction. The influence of the reductant
and temperature on yield and ratio of 3 and 4 were also studied
(entries 4–6). When NaBH4 was used as the reductant, or the tem-
perature of the reduction reaction changed from 25 °C to ꢀ20 °C,
no obvious variation in yields and ratio was observed. Therefore,
the optimal reaction conditions were those outlined in entry 4.
Most of the syntheses known for Jaspine B derive the asymme-
try from the chiral pool of starting materials such as Garner’s alde-
hyde,13 or glucose.14 A well-designed synthesis from
D-xylose was
also reported by Du.15a Unfortunately, the conversion of a mesylate
derivative into an azido intermediate was quite slow and the yield
was not satisfactory,15b as described in other reports.11a,14 To ex-
plore a more economical and practical method, and to continue
our successful efforts in the synthesis of higher carbon sugars
and new amino sugars from
and efficient synthesis of Jaspine B from
D
-xylose,16 herein we report a practical
-xylose.
D
As shown in Scheme 1, Jaspine B can be retrosynthetically dis-
connected into aldehyde 1 according to Du’s method. Aldehyde 1
can be accessed from 2 via hydrolysis. Acetal 2 can be obtained
by benzylation of 3, which, in turn, can be prepared from an 1,2-
azido alcohol derivative 4 through a configuration change of the
⇑
Corresponding author. Tel./fax: +86 371 67781739.
E-mail address: liuhm@zzu.edu.cn (H.-M. Liu).
0008-6215/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2012.01.013

M.-L. Zhao et al. / Carbohydrate Research 351 (2012) 126–129
127
OMe
OMe
OMe
O
O
O
O
C14H29
CHO
OBn
OMe
N3
OH
H2N
OH
N3
N3
OBn
3
1
2
jaspine B
OMe
OMe
OMe
OMe
O
O
O
OH
HO
N3
OH
HO
OH
O
5
4
D-xylose
Scheme 1. Retrosynthetic analysis of Jaspine B.
OMe
OMe
OMe
OMe
O
O
O
O
O
OH
a
O
O
b
c
d
HO
HO
TsO
88%
82%
94%
O
95%
O
N3
OH
HO
HO
OH
TsO
O
5
4
7
6
D-xylose
OMe
OMe
OMe
OMe
O
O
O
O
e
C14H29
f
CHO
OBn
g
91%
ref. 15
86%
85%
N3
N3
OH
OBn
N3
H2N
OH
jaspine B
3 and 4
1
2
Scheme 2. Synthesis of 1. Reagents and conditions: (a) concd H2SO4, acetone, rt, then Na2CO3, rt; (b) tosyl chloride, pyridine, CH2Cl2, rt; (c) methanol, AcCl, reflux, then K2CO3,
rt; (d) NaN3, NH4Cl, H2O/ethanol, reflux; (e) IBX, EtOAc, reflux, then KBH4, ethanol, rt; (f) BnBr, K2CO3, THF, reflux; (g) dioxane, 0.05 mol/L hydrochloric acid, 80 °C.
Table 1
Optimization of the oxidation and reduction reaction of 4 to 3
OMe
OMe
OMe
OMe
OMe
OMe
OMe
OMe
OMe
OMe
O
O
O
O
O
86%
N3
OH
N3
OBn
N3
OBn
N3
O
N3
OH
85%
7%
4
2
3 and 4
2'
Entry
Oxidant
PDC
DMSO and oxalyl chloride
DMSO and acetic anhydride
IBX
IBX
IBX
Reductant
Temperaturea (°C)
Yieldb
Ratioc (3:4)
1
2
3
4
5
6
KBH4
KBH4
KBH4
KBH4
NaBH4
KBH4
25
25
25
25
25
35%
68%
0
86%
85%
86%
12:1
12:1
d
—
12:1
12:1
12:1
ꢀ20
a
b
c
The temperature of reduction reaction.
The crude yield of the mixture of compounds 3 and 4.
Determined by compound 2 and 20.
Not tested.
d
The acetal of 2 was cleaved with 0.05 M hydrochloric acid to af-
ford aldehyde 1 in a 91% yield. Finally, aldehyde 1 was synthesized
in a 42.4% overall yield from -xylose. Jaspine B and its analogues
1. Experimental
1.1. General conditions
D
can be prepared from aldehyde 1 via Wittig reaction.
In summary, we have reported a practically efficient formal
synthesis of Jaspine B in a high yield from inexpensive and easily
available materials and reagents. The synthesis of the analogues
of Jaspine B using this approach is currently underway. The biolog-
ical activity of these analogues will be published elsewhere.
Melting points were measured on a WC-1 melting-point appa-
ratus and are uncorrected. Optical rotations were measured on a
Perkin–Elmer 341 polarimeter at 25 °C. Infrared spectra were re-
corded using KBr discs on a Bruker Vector-22 FTIR spectrometer.
1H and 13C NMR spectra were recorded on a Bruker Advance

128
M.-L. Zhao et al. / Carbohydrate Research 351 (2012) 126–129
DPX-400 spectrometer using CDCl3 as the solvent and TMS as
internal standard. HRMS (high-resolution mass spectra) were ta-
ken with a Q-Tof Micromass spectrometer.
H-1). 13C NMR (101 MHz, CDCl3) d 54.2 (CH3), 55.9 (CH3), 66.8
(CH), 70.4 (CH2), 77.5 (CH), 84.2 (CH), 104.5 (CH). HRMS: calcd
for C7H13N3O4 Na [M+Na]+ 226.0804, found: 226.0809.
1.2. 1,2-O-Isopropylidene-3,5-di-O-p-toluenesulfonyl-
xylofuranose (6)
a
-D
-
1.5. Mixture of (2R,3R,4S)-4-azido-2-dimethoxymethyl-3-
hydroxytetrahydrofuran (3) and (2R,3R,4S)-4-azido-2-
dimethoxymethyl-3-hydroxytetrahydrofuran (4)
A solution of 719 (30.0 g, 158 mmol) and pyridine (38.2 mL,
473 mmol) in CH2Cl2 (300 mL) was cooled to 0 °C, TsCl (75.0 g,
395 mmol) was added to the mixture. After the mixture was stirred
for 24 h at 0 °C to room temperature, saturated NaHCO3 solution
was added, and the reaction mixture was extracted with CH2Cl2.
The organic layer was washed with brine, dried over MgSO4, and
evaporated. Crystallization of the crude product from ethanol gave
compound 6 as a white solid (64.7 g, 82.3%) mp 100.4–102.1 °C;
A solution of the compound 4 (10.0 g, 49.2 mmol), IBX (34.4 g,
123.7 mmol) in EtOAc (200 mL) was heated at reflux for 8 h. The
mixture was filtered and the solids washed with EtOAc. The com-
bined filtrates were evaporated. The residue was dissolved in eth-
anol (150 mL), KBH4 (2.7 g, 49.2 mmol) was added, and the mixture
was stirred at room temperature for 3 h, then quenched by the
addition of saturated NH4Cl aqueous solution. The mixture was
evaporated and the residue was partitioned between EtOAc and
brine, the organic layer was dried over Na2SO4, and concentrated
under vacuum to give the mixture of 3 and 4 as a syrup (8.6 g,
86.1%). This mixture was used in the next step without further
purification.
½
a 2D5
ꢁ
ꢀ30 (c 1.0, CHCl3); IR (KBr); 2932, 1308, 1191, 1176, 1096,
1065, 1051, 994, 841, 713, 666, 551 cmꢀ1 1H NMR (400 MHz,
;
CDCl3) d 1.26 (s, 3H, CH3), 1.42 (s, 3H, CH3), 2.45 (s, 3H, ArCH3),
2.48 (s, 3H, ArCH3), 3.94–4.08 (m, 2H, H-5), 4.33 (td, J = 6.1,
3.0 Hz, 1H, H-4), 4.68 (d, J = 3.6 Hz, 1H, H-2), 4.77 (d, J = 3.0 Hz,
1H, H-3), 5.86 (d, J = 3.6 Hz, 1H, H-1), 7.37 (2d, J = 8.2 Hz, 4H, Ar-
H), 7.75 (2d, J = 8.3 Hz, 4H, Ar-H). 13C NMR (101 MHz, CDCl3) d
21.7 (ArCH3), 21.7 (ArCH3), 26.2 (CMe2), 26.5 (CMe2), 65.9 (CH2),
76.3 (CH), 81.3 (CH), 83.0 (CH), 104.8 (CH), 112.8 (CMe2), 128.0
(ArC), 129.9 (ArC), 130.3 (ArC), 132.2 (ArC), 132.4 (ArC), 145.2
1.6. (2R,3R,4S)-4-Azido-2-dimethoxymethyl-3-
hydroxytetrahydrofuran (3)
A solution of the mixture of 3 and 4 (1.0 g, 4.92 mmol) and pyr-
idine (0.8 mL, 10.0 mmol) in CH2Cl2 (10 mL) was cooled to 0 °C and
then acetic anhydride (0.7 mL, 7.35 mmol) was added to the mix-
ture. After the solution was stirred for 5 h at 0 °C to room temper-
ature, saturated NaHCO3 solution was added, and the reaction
mixture was extracted with CH2Cl2. The organic layer was washed
with brine, dried over MgSO4, and concentrated. The residue was
purified on a silica gel column (petroleum ether–EtOAc 7:1) to
get intermediate I. The material was dissolved in saturated NH3–
CH3OH (10 mL) and the mixture was stirred at room temperature
for 3 h. Then, the mixture was evaporated and the residue was
purified on a silica gel column (petroleum ether–EtOAc 1.5:1) to
(ArC), 145.9 (ArC). HRMS: calcd for
521.0919, found: 521.0915.
C
14H19N3O4Na [M+Na]+
1.3. (2R,3R,4R)-2-Dimethoxymethyl-3,4-epoxytetrahydrofuran
(5)
A solution of the compound 6 (30.0 g, 60.2 mmol) in dry meth-
anol (500 mL) containing AcCl (2.50 mL, 35.5 mmol) was heated at
reflux for 24 h. The mixture was cooled to room temperature and
stirred with anhydrous calcium carbonate (15.0 g, 108.5 mmol)
overnight. The mixture was filtered and the solids washed with
CH2Cl2. The combined filtrates were evaporated and the residue
was partitioned between CH2Cl2 and brine, the organic layer was
dried over MgSO4, and concentrated under vacuum to give 5 as a
syrup (9.1 g, 94.2%). This compound was used in the next step
without further purification. A small sample was purified on a sil-
ica gel column (petroleum ether–EtOAc 1:1) to provide pure 5:
give pure 3: ½a 2D5
ꢁ
ꢀ10 (c 1.0, CHCl3); IR (KBr); 3461, 2938, 2103,
1737, 1216 cmꢀ1
.
1H NMR (400 MHz, CDCl3) d 3.18 (s, 1H, OH)
3.44 (s, 3H, CH3), 3.46 (s, 3H, CH3), 3.86–4.04 (m, 4H, H-5b, H-5 ,
a
H-4, H-2), 4.42 (s, 1H, H-3), 4.61 (d, J = 6.7 Hz, 1H, H-1). 13C NMR
(101 MHz, CDCl3) d 54.5 (CH3), 55.3 (CH3), 62.5 (CH), 68.8 (CH2),
72.7 (CH), 79.9 (CH), 103.2 (CH). HRMS: calcd for C7H13N3O4 Na
[M+Na]+ 226.0804, found: 226.0801.
½
a 2D5
+26 (c 1.1, CHCl3); IR (KBr); 3467, 2941, 1737, 1713, 1365,
ꢁ
1201, 908, 854 cmꢀ1.1H NMR (400 MHz, CDCl3) d 3.44 (s, 3H,
CH3), 3.46 (s, 3H, CH3), 3.76 – 3.88 (m, 3H, H-3, H-4, H-5b), 3.98
1.7. (2R,3S,4S)-4-Azido-2-dimethoxymethyl-3-benzyloxytetrahy
drofuran (2) and (2R,3R,4S)-4-azido-2-dimethoxymethyl-3-
benzyloxytetrahydrofuran (20)
(d, J = 10.1 Hz, 1H, H-5 ), 4.08 (d, J = 4.4 Hz, 1H, H-2), 4.29 (d,
a
J = 4.4 Hz, 1H, H-1). 13C NMR (101 MHz, CDCl3) d 55.3 (CH3), 56.2
(CH3), 56.5 (CH), 56.7 (CH), 67.9 (CH2), 77.6 (CH), 104.8 (CH).
HRMS: calcd for C7H12O4Na [M+Na]+ 183.0633, found: 183.0636.
A solution of the mixture of 3 and 4 (6.0 g, 29.5 mmol), calcium
carbonate (4.1 g, 29.5 mmol) and benzyl bromide (6.0 g,
35.4 mmol) in THF (100 mL) was heated at reflux for 5 h. The mix-
ture was filtered and the solids washed with EtOAc. The combined
filtrates were evaporated and the residue was partitioned between
EtOAc and brine, the organic layer was dried over Na2SO4, and con-
centrated under vacuum. The residue was purified on a silica gel
column (petroleum ether–EtOAc, 7:1) to afford 2 (7.4 g, 85.3%)
1.4. (2R,3R,4S)-4-Azido-2-dimethoxymethyl-3-
hydroxytetrahydrofuran (4)
A solution of epoxide 5 (10.0 g, 62.5 mmol), sodium azide (8.1 g,
124.6 mmol) and ammonium chloride (10.0 g, 188.7 mmol) in 95%
ethanol (200 mL) was heated at reflux for 24 h. The residue formed
after evaporation was extracted with CH2Cl2. The organic layer was
dried over MgSO4, and concentrated under vacuum to give 4 as a
syrup (12.1 g, 95.4%). This compound was used in the next step
without further purification. A small sample was purified on a sil-
ica gel column (petroleum ether–EtOAc, 1.5:1) to obtain pure 4:
and 20 (0.62 g, 7.2%) as a syrup. Compound 2: ½a 2D5
ꢁ
+55 (c 1.0, CHCl3);
Rf 0.3 (petroleum ether–EtOAc 5:1); IR (KBr); 3446, 2941, 2100,
.
1082, 781 cmꢀ1 1H NMR (400 MHz, CDCl3) d 3.38 (s, 3H, CH3),
3.45 (s, 3H, CH3), 3.84 (td, J = 7.6, 4.7 Hz, 1H, H-4), 3.94 (dd,
J = 7.7, 4.2 Hz, 1H, H-3), 3.98–4.09 (m, 2H, H-5, H-5 ), 4.20 (t,
a
½
a 2D5
ꢁ
+30 (c 1.0, CHCl3); IR (KBr); 3410, 2940, 2100, 1668,
1085 cmꢀ1 1H NMR (400 MHz, CDCl3) d 3.01 (s, 1H, OH), 3.45 (s,
3H, CH3), 3.48 (s, 3H, CH3), 3.77 (dd, J = 6.2, 5.0 Hz, 1H, H-2), 3.86
J = 4.4 Hz, 1H, H-2), 4.61–4.72 (m, 2H, CH2Ph), 4.84 (d, J = 11.2 Hz,
1H, H-1), 7.30–7.49 (m, 5H, Ar-H). 13C NMR (101 MHz, CDCl3) d
53.5 (CH3), 55.0 (CH3), 61.5 (CH), 68.7 (CH2), 74.4 (CH2), 79.8
(CH), 80. 0(CH), 102.2 (CH), 127.9 (ArC), 127.9 (ArC), 128.4 (ArC),
137.6 (ArC). HRMS: calcd for C14H19N3O4Na [M+Na]+: 316.1273,
.
(dd, J = 9.6, 3.9 Hz, 1H, H-5 ), 3.95–4.01 (m, 1H, H-4), 4.06 (dd,
a
J = 9.6, 5.7 Hz, 1H, H-5), 4.22 (s, 1H, H-3), 4.39 (d, J = 6.3 Hz, 1H,

M.-L. Zhao et al. / Carbohydrate Research 351 (2012) 126–129
129
found: 316.1277. Compound 20: ½a D25
ꢁ
+38 (c 1.0, CHCl3); Rf 0.7
(petroleum ether–EtOAc 5:1); IR (KBr); 2937, 2100, 1095, 738,
6. Yoshimitsu, Y.; Oishi, S.; Miyagaki, J.; Inuki, S.; Ohno, H.; Fujii, N. Bioorg. Med.
Chem. 2011, 19, 5402–5408.
7. For a review, see Abraham, E.; Davies, S. G.; Roberts, P. M.; Russell, A. J.;
Thomson, J. E. Tetrahedron: Asymmetry 2008, 19, 1027–1047.
698 cmꢀ1 1H NMR (400 MHz, CDCl3) d 3.45 (s, 3H, CH3), 3.47 (s,
;
8. (a) van den Berg, R. J. B. H. N.; Boltje, T. J.; Verhagen, C. P.; Litjens, R. E. J. N.; van
der Marel, G. A.; Overkleeft, H. S. J. Org. Chem. 2006, 71, 836–839; (b) Lee, T.;
Lee, S.; Kwak, Y. S.; Kim, D.; Kim, S. Org. Lett. 2007, 9, 429–432.
9. (a) Prasad, K. R.; Chandrakumar, A. J. Org. Chem. 2007, 72, 6312–6315; (b)
Ichikawa, Y.; Matsunaga, K.; Masuda, T.; Kotsuki, H.; Nakano, K. Tetrahedron
2008, 64, 11313–11318; (c) Reddipalli, G.; Venkataiah, M.; Mishra, M. K.;
Fadnavis, N. W. Tetrahedron: Asymmetry 2009, 20, 1802–1805; (d) Prasad, K. R.;
Penchalaiah, P. Tetrahedron: Asymmetry 2011, 22, 1400–1403.
3H, CH3), 3.95–4.07 (m, 5H, H-4, H-3, H-2, H-5, H-5 ), 4.37 (d,
a
J = 6.3 Hz, 1H, H-1), 4.63 (q, J = 11.8 Hz, 2H, CH2Ph), 7.30–7.42 (m,
5H, Ar-H). 13C NMR (101 MHz, CDCl3) d 54.1 (CH3), 55.5 (CH3),
65.7 (CH), 70.9 (CH2), 72.1 (CH2), 84.2 (CH), 84.5 (CH), 103.8 (CH),
128.0 (ArC), 128.0 (ArC), 128.5 (ArC), 137.3 (ArC). HRMS: calcd for
C
14H19N3O4Na [M+Na]+ 316.1273, found: 316.1273.
10. (a) Bhaket, P.; Morris, K.; Stauffer, C. S.; Datta, A. Org. Lett. 2005, 7, 875–876; (b)
Vichare, P.; Chattopadhyay, A. Tetrahedron: Asymmetry 2010, 21, 1983–1987;
(c) Rao, G. S.; Sudhakar, N.; Rao, B. V.; Basha, S. J. Tetrahedron: Asymmetry 2010,
21, 1963–1970; (d) Rao, G. S.; Rao, B. V. Tetrahedron Lett. 2011, 52, 6076–6079.
11. (a) Reddy, L. V. R.; Reddy, P. V.; Shaw, A. K. Tetrahedron: Asymmetry 2007, 18,
542–546; (b) Sánchez-Eleuterio, A.; Quintero, L.; Sartillo-Piscil, F. J. Org. Chem.
2011, 76, 5466–5471; (c) Rao, G. S.; Rao, B. V. Tetrahedron Lett. 2011, 52, 4861–
4864.
12. (a) Ribes, C.; Falomir, E.; Carda, M.; Marco, J. A. Tetrahedron 2006, 62, 5421–
5425; (b) Génisson, Y.; Lamandé, L.; Salma, Y.; Andrieu-Abadie, N.; André, C.;
Baltas, M. Tetrahedron: Asymmetry 2007, 18, 857–864; (c) Abraham, E.;
Candela-Lena, J. I.; Davies, S. G.; Georgiou, M.; Nicholson, R. L.; Roberts, P.
M.; Russell, A. J.; Sánchez-Fernández, E. M.; Smith, A. D.; Thomson, J. E.
Tetrahedron: Asymmetry 2007, 18, 2510–2513; (d) Yakura, T.; Sato, S.;
Yoshimoto, Y. Chem. Pharm. Bull. 2007, 55, 1284–1286; (e) Venkatesan, K.;
Srinivasan, K. V. Tetrahedron: Asymmetry 2008, 19, 209–215; (f) Abraham, E.;
Brock, E. A.; Candela-Lena, J. I.; Davies, S. G.; Georgiou, M.; Nicholson, R. L.;
Perkins, J. H.; Roberts, P. M.; Russell, A. J.; Sánchez-Fernández, E. M.; Scott, P.
M.; Smith, A. D.; Thomson, J. E. Org. Biomol. Chem. 2008, 6, 1665–1673; (g)
1.8. (2R,3S,4S)-4-Azido-3-(benzyloxy)tetrahydrofuran-2-
carbaldehyde (1)
A solution of 2 (3.0 g, 10.2 mmol) in dioxane (10 mL) and 0.05 M
hydrochloric acid (30 mL) was stirred at 80 °C for 3 h. The mixture
was neutralized with saturated aqueous sodium carbonate and ex-
tracted with CH2Cl2, the organic layer was washed with brine,
dried over Na2SO4, and concentrated under vacuum. The residue
was purified on a silica gel column (petroleum ether–EtOAc 5:1)
to afford 1 (2.3 g, 90.8%): ½a D25
ꢁ
+27 (c 0.2, CHCl3); 1H NMR
(400 MHz, CDCl3) d 4.06 (m, 3H), 4.32 (dd, J = 6.9, 1.8 Hz, 1H),
4.53 (dd, J = 6.7, 4.5 Hz, 1H), 4.70, 4.73 (2d, J = 11.7 Hz, 2H, CH2Ph),
7.30–7.49 (m, 5H, ArH), 9.69 (d, J = 1.9 Hz, 1H, CHO). 13C NMR
(101 MHz, CDCl3) d 61.0 (CH), 70.5 (CH2), 73.7 (CH2), 81.5 (CH),
82.4 (CH), 128.0 (ArC), 128.3 (ArC), 128.6 (ArC), 136.6 (ArC),
200.5 (CHO). HRMS: calcd for C14H19N3O4Na [M+Na]+ 270.0855,
found: 270.0857.
ˇ
Enders, D.; Terteryan, V.; Palecek, J. Synthesis 2008, 14, 2278–2282; (h) Urano,
H.; Enomoto, M.; Kuwahara, S. Biosci. Biotechnol. Biochem. 2010, 74, 152–157;
(i) Salma, Y.; Ballereau, S.; Maaliki, C.; Ladeira, S.; Andrieu-Abadieb, N.;
Génisson, Y. Org. Biomol. Chem. 2010, 8, 3227–3243; (j) Llaveria, J.; Díaz, Y.;
Matheu, M. I.; Castillón, S. Eur. J. Org. Chem. 2011, 1514–1519; (k) Salma, Y.;
Ballereau, S.; Ladeira, S.; Lepetit, C.; Chauvin, R.; Andrieu-Abadie, N.; Génisson,
Y. Tetrahedron 2011, 67, 4253–4262; (l) Ballereau, S.; Andrieu-Abadie, N.;
Saffon, N.; Génisson, Y. Tetrahedron 2011, 67, 2570–2578.
Acknowledgment
13. (a) Sudhakar, N.; Kumar, A. R.; Prabhakar, A.; Jagadeesh, B.; Rao, B. V.
Tetrahedron Lett. 2005, 46, 325–327; (b) Passiniemi, M.; Koskinen, A. M. P.
Tetrahedron Lett. 2008, 49, 980–983; (c) Inuki, S.; Yoshimitsu, Y.; Oishi, S.; Fujii,
N.; Ohno, H. Org. Lett. 2009, 11, 4478–4481; (d) Inuki, S.; Yoshimitsu, Y.; Oishi,
S.; Fujii, N.; Ohno, H. J. Org. Chem. 2010, 75, 3831–3842; (e) Yoshimitsu, Y.;
Inuki, S.; Oishi, S.; Fujii, N.; Ohno, H. J. Org. Chem. 2010, 75, 3843–3846; (f)
Passiniemi, M.; Koskinen, A. M. P. Org. Biomol. Chem. 2011, 9, 1774–1783.
14. (a) Chandrasekhar, S.; Tiwari, B.; Prakash, S. J. ARKIVOC 2006, 155–161;
(b) Ramana, C. V.; Giri, A. G.; Suryawanshi, S. B.; Gonnade, R. G. Tetrahedron
Lett. 2007, 48, 265–268; (c) Jayachitra, G.; Sudhakar, N.; Anchoori, R. K.; Rao,
B. V.; Roy, S.; Banerjeeb, R. Synthesis 2010, 1, 115–119; Cruz-Gregorio, S.;
Espinoza-Rojas, E.; Quintero, L.; Sartillo-Piscil, F. Tetrahedron Lett. 2011, 52,
6370–6371.
We are grateful for the financial support from the National Nat-
ural Science Foundation of China (Project No. 81172937).
Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.carres.2012.01.013.
References
15. (a) Du, Y.; Liu, J.; Linhardt, R. J. J. Org. Chem. 2006, 71, 1251–1253; (b) Liu, J.; Du,
Y.; Dong, X.; Meng, S.; Xiao, J.; Cheng, L. Carbohydr. Res. 2006, 341, 2653–2657.
16. (a) Liu, H. M.; Zou, D. P.; Zhang, F. Y.; Zhu, W. G.; Peng, T. Eur. J. Org. Chem. 2004,
10, 2103–2106; (b) Zou, D. P.; Cao, S. X.; Xu, W. C.; Liu, H. M. Carbohydr. Res.
2005, 340, 2411–2421; (c) Ji, X. M.; Mo, J.; Liu, H. M.; Sun, H. P. Carbohydr. Res.
2006, 341, 2312–2320.
1. Kuroda, I.; Musman, M.; Ohtani, I. I.; Ichiba, T.; Tanaka, J.; Gravalos, D. G.; Higa,
T. J. Nat. Prod. 2002, 65, 1505–1506.
2. Ledroit, V.; Debitus, C.; Lavaud, C.; Massiot, G. Tetrahedron Lett. 2003, 44, 225–
228.
3. Canals, D.; Mormeneo, D.; Fabriàs, G.; Llebaria, A.; Casas, J.; Delgado, A. Bioorg.
Med. Chem. 2009, 17, 235–241.
4. Salma, Y.; Lafont, E.; Therville, N.; Carpentier, S.; Bonnafé, M. J.; Levade, T.;
Génisson, Y.; Andrieu-Abadie, N. Biochem. Pharmacol. 2009, 78, 477–485.
5. Salma, Y.; Ballereau, S.; Maaliki, C.; Ladeira, S.; Andrieu-Abadie, N.; Génisson, Y.
Org. Biomol. Chem. 2010, 8, 3227–3243.
17. Talekar, R. R.; Wightman, R. H. Tetrahedron 1997, 53, 3831–3842.
18. Yu, H. W.; Zhang, H. Y.; Yang, Z. J.; Min, J. M.; Ma, L. T.; Zhang, L. H. Pure Appl.
Chem. 1998, 70, 435–438.
ˇ
ˇ
19. Moravcová, J.; Capková, J.; Stanek, J. Carbohydr. Res. 1994, 263, 61–66.