Synthesis of a library of allyl α-l-arabinofuranosyl-α- or β-d-xylopyranosides; route to higher oligomers

Article abstract of DOI:10.1016/j.carres.2007.08.007

Six isomeric disaccharides allyl 2,3,5-tri-O-benzoyl-α-l-arabinofuranosyl-α-d-xylopyranosides and β-d-xylopyranosides were synthetized by the stereoselective glycosylation of pure allyl α- or β-d-xylopyranosides with 1-O-acetyl-2,3,5-tri-O-benzoyl-l-arabi

Full text of DOI:10.1016/j.carres.2007.08.007

Available online at www.sciencedirect.com
Carbohydrate Research 342 (2007) 2649–2656
Note
Synthesis of a library of allyl a-L-arabinofuranosyl-a-
or b-D-xylopyranosides; route to higher oligomers
Jean-Pierre Utille*,ꢀ and Isabelle Jeacomine
Centre de Recherches sur les Macromole´cules Ve´ge´tales (CERMAV-CNRS),ꢁ BP53, 38041 Grenoble cedex 9, France
Received 16 February 2007; received in revised form 8 July 2007; accepted 17 August 2007
Available online 24 August 2007
Dedicated to Professor A. S. Perlin on the occasion of his 85th year
Abstract—Six isomeric disaccharides allyl 2,3,5-tri-O-benzoyl-a-L-arabinofuranosyl-a-D-xylopyranosides and b-D-xylopyranosides
were synthetized by the stereoselective glycosylation of pure allyl a- or b-D-xylopyranosides with 1-O-acetyl-2,3,5-tri-O-benzoyl-
L-arabinofuranose as donor, catalyzed with BF3ÆEt2O in DCM. Regio- and stereoselective glycosylation with excess of donor fur-
nished almost exclusively the trisaccharides allyl 2,3-di-O-(2,3,5-tri-O-benzoyl-a-L-arabinofuranosyl)-a- or b-D-xylopyranosides.
Extension of the reaction to the triol b-D-xylopyranosyl-(1!4)-1,2,3-tri-O-acetyl-a-D-xylopyranose, obtained from the 4-hydroxyl
penta-O-acetyl-a-xylobiose, gave in the same manner the tetrasaccharide [2,3-di-O-(2,3,5-tri-O-benzoyl-a-L-arabinofuranosyl)-b-D-
xylopyranosyl]-(1!4)-1,2,3-tri-O-acetyl-a-D-xylopyranose. The protocol described herein should offer the possibility to produce
branched oligosaccharides with a 2,3-di-O-(a-L–Araf)-b-D-Xylp block unit at the terminal non-reducing end.
Ó 2007 Elsevier Ltd. All rights reserved.
Keywords: a-L-Arabinofuranosyl-D-xylopyranosides; Library; Oligosaccharides
General methods for the synthesis of di- and oligosac-
charides have developed considerably throughout the
last 20 years, but oligosaccharide preparation through
chemical syntheses is still a tedious task. In order to
shorten the route towards the preparation of L-arabino-
furanosyl-D-xylopyranosyl oligosaccharides, we rea-
soned that regio- and stereoglycosylation of
unprotected allyl a or b-D-xylopyranoside acceptors by
a 2,3,5-tri-O-benzoyl-L-arabinofuranosyl donor should
offer a direct way to the six possible allyl a-L-arabinofur-
anosyl-a- or b-D-xylopyranoside disaccharides. Further-
more, our hypothesis was that the use of an excess of the
donor should lead to a preferential trimer (a-L-Araf)2–b-
D-Xylp as the consequence of the different reactivities of
the acceptor hydroxyl-groups. The a-L-Araf–b-D-Xylp
oligosaccharides belong to the arabinoxylan family,
which represent a considerable part of the building
blocks of the cell wall in cereals.1–7 The polymer back-
bone consists of b-(1!4)-linked-D-xylopyranosyl units,
which are unsubstituted or to a variable extent, mono
or di-substituted with a-L-Araf moities. Occasionally
a-L-Araf are substituted at the C-5 position by ferulic
or coumaric esters.8 Few reports9–12a show the difficul-
ties of preparing the L-Araf-D-Xylp block unit by chem-
ical synthesis. The procedure adopted in our report is
amenable to a library of dimers and would design a
way to the series of linear D-xylo-oligosaccharides,
substituted regiospecifically both at the C-2 and C-3
positions of the non-reducing end residue by a-L-Araf
moities. We illustrate our strategy by the synthesis of
the six isomeric disaccharides, the trimers, allyl 2,3-
di-O-(a-L-arabinofuranosyl)-a- and b-D-xylopyrano-
sides and tetramer [2,3-di-O-(a-L-arabinofuranosyl)-
b-D-xylopyranosyl]-(1!4)-D-xylopyranose.
*
Corresponding author. Tel.: +33 4 76 03 76 66; fax: +33 47 654
7203; e-mail: jean-pierre.utille@cermav.cnrs.fr
ꢀ Post-doctoral researcher at Mc Gill university in 1981/82.
ꢁ
The donor, namely, 1-O-acetyl-2,3,5-tri-O-benzoyl-
L-arabinofuranose a/b (9:1) 213 was prepared by
´
Universite Joseph Fourier, and member of the Institut de Chimie
´
Moleculaire de Grenoble.
0008-6215/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2007.08.007

2650
J.-P. Utille, I. Jeacomine / Carbohydrate Research 342 (2007) 2649–2656
conventional means from methyl L-arabinofuranoside.14
For glycosylation reactions, donor 2 in dry DCM solu-
tion was allowed to react, in presence of BF3ÆEt2O, with
the triols a12b,c or b12a-D-xylopyranoside 3, 4. In the case
of allyl b-D-xylopyranoside acceptor 4, the products
formed during the reaction show well-dispersed TLC
indicating that easy separation of the products should
be possible (Scheme 1).
In a typical chromatography run, the elution of the
reaction mixture on a silica gel column with solvent (tol-
uene/EtOAc from 9:1 to 3:2) successively led to, first
unreacted donor 2, traces of hydrolyzed donor, then
the fast running trisaccharide 12, resulting from the L-
Araf coupling both at C-2 and C-3 of the b-D-Xylp entity
4, then the a-L-(1!3)- linked L-Araf-D-xyloside dimer 8,
followed by the a-L-(1!4)-linked disaccharide 9, and
the a-L-(1!2)-linked dimer 10. The amounts of 12, 8,
9 and 10 obtained for 1.5 equiv of donor 4, were in
the ratio (ꢀ1:6:2:1). Meanwhile, the same experiment
with an excess of donor (2.3 equiv) led to 12 as the major
product (12, 8, 9, 10 ꢀ12:6:1:1); the high stereospecific-
ity of the reaction was noted and no traces of b-L-linked
products were detected by NMR.15 The structures of the
isolated compounds were characterized by 1H
(400 MHz) and 13C NMR (100 MHz) spectroscopy by
1D and 2D experiments and the linkage sites were con-
2 + 4
(i)
O
O
R4O
O
O
R4O
OAll
O
OR2
4
O
O
3
O
OAll
R O
R3O
OAll
R O
OAll
O
OR2
O
+
+
+
O
OR
O
OR
O
OR
OR
RO
O
OR
OR
RO
RO
RO
OR
RO
OR
OR
OR
12 R=Bz, R4=H
12a R=Bz, R4=Ac
12b R=R4=H
8
R=Bz, R2=R4=H
9
R=Bz, R2=R3=H
10 R=Bz, R3=R4=H
10a R=Bz, R3=R4=Ac
10b R=R3=R4=H
(ii)
(ii)
(ii)
(ii)
(v)
8a R=Bz, R2=R4=Ac
8b R=R2=R4=H
9a R=Bz, R2=R3=Ac
9b R=R2=R3=H
(iii)
(iii)
(iii)
(iii)
9c R=Bz, R2=Ac, R3=H
10c R=Bz, R3=Ac, R4=H
(iv)
Scheme 1. Reagents and conditions: (i) CH2Cl2, BF3ÆEt2O, rt, 2 h; silica gel chromatography: toluene–EtOAc; (ii) Ac2O, py, rt, 16 h, ꢀquant; (iii)
NaOMe, MeOH, rt, 16 h,25 ꢀquant; (iv) Ac2O, py, 1.3 equiv, rt, 16 h, 65%; (v) lipase: Candida antartica, isopropanol, 18 h, 50 °C, 98%.
2 + 3
(i)
O
R4O
O
R4O
O
4
O
O
3
O
R O
R3O
+
+
+
R O
O
O
OR2
O
OAll
O
OR
OR2
OAll
O
OR
O
OR
OAll
OAll
O
OR
RO
O
OR
OR
RO
RO
RO
OR
RO
OR
OR
OR
11 R=Bz, R4=H
5a R=Bz, R2=R4=H
5a R=Bz, R2=R4=Ac
5b R=R2=R4=H
6
R=Bz, R2=R3=H
7
R=Bz, R3=R4=H
(ii)
(ii)
(ii)
(ii)
11a R=Bz, R4=Ac
11b R=R4=H
6a R=Bz, R2=R3=Ac
6b R=R2=R3=H
7a R=Bz, R3=R4=Ac
7b R=R3=R4=H
(iii)
(iii)
(iii)
(iii)
7c R=Bz, R3=H, R4=Ac
13 R=Bz, R4=2,3,5-tri-
O-Bz-α-L-Araf
(iv)
Scheme 2. Reagents and conditions: (i) DCM, BF3ÆEt2O, rt, 2 h; silica gel chromatography: toluene–EtOAc; (ii) Ac2O, py, rt, 16 h, ꢀquant; (iii)
NaOMe, MeOH, rt, 16 h,25 ꢀquant; (iv) lipase: Candida antartica, EtOAc, 48 h, 50 °C, 98%.

J.-P. Utille, I. Jeacomine / Carbohydrate Research 342 (2007) 2649–2656
2651
firmed by studying the effects of the chemical shifts be-
tween the acetylated and non-acetylated derivatives 12,
8, 9 and 10 (discussed thereafter). Coupling of donor 2
with allyl a-D-xylopyranoside 3 under the same condi-
tions (1.5 equiv) gave in TLC a quite similar resolved
pattern: the order of elution being, respectively, trisac-
charide 11 then the a-L-(1!3)-linked dimer 5, followed
by the couple of 6 and 7 (Scheme 2).
being the result of selective removal17,18 of the 40-O-
acetyl group of hexa-O-acetyl-a-xylobiose by immobi-
lized lipase Candida antartica17 in isopropanol. 15 was
obtained in a fairly good yield (50%) and tetrasaccharide
16 was prepared in the same manner with 2.3 equiv of
donor 2 with a 60% yield; NMR spectroscopy confirmed
the regio- and stereospecificity of the substitution at C-20
and C-30 of 15, and the resulting product 16 was easily
separated on a silica gel column.
Further experiments of selective acetylation on 6 and
7 by lipase Candida antartica16 in dry EtOAc as
acylating reagent produced the 4-O-acetyl- derivative
a-L-(1!2)-linked 7c, while the a-L-(1!4)-linked 6 was
not affected, and separation was much easier via this
method. It is worth noting that 11, conserved the stereo-
and regiospecificity observed for 12 with 2,3-di-O-L-Araf
substitution of the a-D-xylopyranoside unit 3. Further-
more, coupling with 2.3 equiv of donor 2, gave after
chromatography, a pure tetrasaccharide 13 with a tri-
substitution at C-2, C-3 and C-4 of the acceptor 3 show-
ing less steric hindrance of the 4-hydroxyl group on 11,
in comparison with the same site on the b-D-xylopyran-
oside unit of 12. This observation should lead to an eas-
ier chain elongation of the D-Xylp backbone from the
non-reducing end. In another experiment, we studied
the coupling of donor 2 with the triol 1,2,3-tri-O-acet-
yl-a-xylobiose derivative 15 (Scheme 3).
NMR spectroscopy: All new compounds (1–16) were
fully characterized by 1H (400 MHz) and 13C NMR
(100 MHz) spectroscopy, several reports19–24 having
dealt with numerous data concerning Araf–Xylp 1H
and/or 13C NMR studies. The a-L-Araf configuration
1
in 5–13 and 16 was proved by H NMR spectroscopy
from the J1,2 values (<1.8 Hz), which were in agreement
with those given by Mitsutani et al.15 The structures of
5–12 were determined both through their acetylated
derivatives 5a–12a by 1H NMR with the downfield shift
observed for the proton signals on the esterified sites
(Table 1) and by 13C NMR, by examining the signal
shifts for the carbons belonging to the glycosidic bonds
(Table 2).
For example, the presence of unprotected OH groups
at C-2 and C-4 of 5 was confirmed by acetylation: in the
1H NMR spectrum of diacetate 5a, the signals for H-2
and H-4 had shifted downfield, respectively, to d 4.87
and 4.99 compared with the positions at 3.74 and
3.70 in the spectrum of 5 (Dd 1.13 and 1.29). In the same
manner, the spectra of 6–12 and 6a–12a offered compa-
rable chemical shifts (Table 1). In the 13C NMR spectra,
the formation of glycosidic bonds shows downfield shifts
of the glycosidic carbon signal between 5.42 and
11.65 ppm. For example, with compound 8 (1!3)-
linked, the C-3 signal shifted from 76.41 for triol 4 to
This compound was prepared by the selective removal
of the 20- and 30-O-acetyl groups by treating the penta-
O-acetyl derivative 14 with DCM/MeOH/K2CO3; 14
O
O
HO
AcO
O
AcO
OAc
OAc
OAc
14
(i)
Table 1. 1H NMR: chemical shifts (DdH-Xyl) resulting from the
acetylation of 5–12
H-1
H-2
H-3
H-4
H-5a H-5b
O
O
HO
HO
O
AcO
5 (1!3)
Dd5aꢁ5
4.91
3.74
3.76
3.70
3.77
3.77
3.68
4.05
4.09
4.04
3.72
4.07
3.58
3.63
3.57
3.23
3.50
3.38
3.58
3.27
OH
OAc
(0.12) (1.13) (0.52) (1.29)
OAc
6 (1!4)
4.85
5.01
4.32
4.52
4.61
4.99
4.39
3.57
(1.20) (1.68) (0.23)
3.52 3.98 3.72
(0.19) (1.56) (1.21)
3.59 3.50 3.74
(1.49) (0.42) (1.25)
3.52 3.79 3.82
(1.38) (1.41) (0.20)
3.70 3.78 3.70
(0.12) (1.51) (1.20)
3.84
3.74
Dd6aꢁ6
(ii)
15
7 (1!2)
Dd7aꢁ7
8 (1!3)
Dd8aꢁ8
O
9 (1!4)
Dd9aꢁ9
O
HO
O
O
AcO
O
OAc
10 (1!2)
Dd10aꢁ10
11 (1!2; 1!3)
Dd11aꢁ11
12 (1!2; 1!3)
Dd12aꢁ12
OR
OAc
O
RO
16
O
OR
3.80
4.03
(0.35) (1.19)
3.76 3.74
(0.35) (1.25)
3.74
OR
RO
3.91
OR
R = Bz
Scheme 3. Coupling reaction of donor
xylobiose derivative 15.
2 with the tri-O-acetyl
Dd 6 0.10 are neglected 5a–10a (di-O-acetyl); 11a and 12a (mono-O-
acetyl).

2652
J.-P. Utille, I. Jeacomine / Carbohydrate Research 342 (2007) 2649–2656
Table 2. 13C NMR: chemical shifts (DdC-Xyl) resulting from the
glycosylation of 3 and 4
ence. Analytical thin layer chromatography (TLC) was
performed on pre-coated plates (Silica Gel, 60F254
,
C-1
98.13
97.06
C-2
71.90
71.23
C-3
73.86
84.53
C-4
70.05
69.39
C-5
61.84
59.44
E. Merck Co.) and the products were visualized with
H2SO4/EtOH/H2O (15:15:1) by charring. Silica Gel 60
(E. Merck Co.) was employed for flash chromatogra-
phy. Optical rotations were measured at 20 °C in a 1-
dm cell on a Perkin–Elmer 341 polarimeter. All solvents
and reagents were purified according to standard proce-
3 All a-D-Xylp
5 (1!3)
Dd5ꢁ3
(ꢁ1.07) (ꢁ0.67) (10.67) (ꢁ0.66) (ꢁ2.40)
6 (1!4)
97.10
(ꢁ1.03)
97.46
72.24
(0.34) (ꢁ0.53)
80.31 73.20
73.33
76.84
(6.79) (ꢁ2.40)
70.11 61.08
(0.06) (ꢁ0.76)
69.50 61.33
59.44
Dd6ꢁ3
7 (1!2)
Dd7ꢁ3
dures. Melting points were determined on a Buchi 535
¨
(ꢁ0.67)
(8.41) (ꢁ0.66)
11 (1!2; 1!3)
97.62
77.32
(5.42)
73.66
72.66
82.17
apparatus and are uncorrected. ESI mass spectra were
obtained on a Waters micromass ZQ mass spectrometer.
Enzymic acetylation (dry EtOAc) or deacetylation (iso-
propanol) were performed with lipase from Candida
antartica (Novozym 435, Sigma). Derivatizations: for
some compounds mono-or di-O-acetylation or de-acyla-
tion were worked up as indicated; all the products were
characterized (see Supplementary data).
Dd11ꢁ3
(ꢁ0.51)
102.71
102.17
(8.31) (ꢁ0.55) (ꢁ0.51)
4 All b-D-Xylp
8 (1!3)
Dd8ꢁ4
76.41
86.68
69.85
68.52
65.76
65.28
(ꢁ0.54) (ꢁ1.00) (10.27) (ꢁ1.33) (ꢁ0.48)
101.31 71.64 72.54 76.06 61.21
(6.21) (ꢁ4.55)
69.71 63.80
(3.08) (ꢁ0.73) (ꢁ0.14) (ꢁ1.96)
74.62 88.06 69.30 65.28
(ꢁ1.52) (0.96) (11.65) (ꢁ0.55) (ꢁ0.48)
9 (1!4)
Dd9ꢁ4
(ꢁ1.40) (ꢁ2.02) (ꢁ3.87)
10 (1!2)
Dd10ꢁ4
100.07
76.74
75.68
(ꢁ2.64)
12 (1!2; 1!3) 101.19
Dd12ꢁ4
1.2. 1-O-Acetyl-2,3,5-tri-O-benzoyl-a-L-arabinofuranose
213
86.68 for 8 (Dd 10.27 ppm); similars effects were ob-
served for all the other products (Table 2).
1.3. Allyl a,b-D-xylopyranoside 3, 412
In conclusion, we have shown a convenient method
for accessing to 2,3-di-O-L-Araf-substitued-D-Xylp enti-
ties, giving by this pathway a strategy for the synthesis
of a-L-Araf-D-Xylp oligosaccharides. The reaction had
both good regio- and stereoselectivities. The large scale
production of a-L-Araf-D-Xylp disaccharides was shown
to be easier by glycosylation of allyl b-D-xylopyranoside
4, which led to convenient chromatographic separation
of the a-(1!2)-, -(1!3)-, -(1!4)-linked isomers. The
use of allyl a-D-xylopyranoside 3 as acceptor was less
practical since the a-(1!2)- and -(1!4)-linked disaccha-
rides had similar chromatographic behaviour. Further-
more, we showed that 1-O-acetyl-2,3,5-tri-O-benzoyl-a-
L-arabinofuranose was a stable and effective glycosyl
donor. We expected that the present synthetic scheme
would be useful for chain elongation by adding b-D-Xylp
unit(s) onto the terminal unprotected 4-hydroxyl group
of structures like 11 and 12.
1.4. Coupling reactions: with allyl a-D-xylopyranoside 3
1.4.1. 1.5 equiv of donor 2. Compound 3 (190 mg,
1 mmol) was dissolved in dry DCM (3 mL), then 2
(756 mg, 1.5 mmol) was added. The solution was cooled
in an ice-water bath and after 15 min stirring, addition
of BF3ÆEt2O (50 lL) was performed. After 2 h more stir-
ring, TLC indicated that the reaction was quite com-
plete: traces of 3 (EtOAc, Rf 0.25) and presence of 4
spots, respectively, with Rf: 0.75, 0.72, 0.53, 0.19 (3:2 tol-
uene/EtOAc) corresponding, respectively, to donor 2,
trisaccharide 11, the major product a-(1!3)-linked
disaccharide 5, then a mixture of a-(1!4)-, a-(1!2)-
linked dimers 6, 7. The reactional mixture was diluted
with DCM, neutralized with Et3N, washed with satd
NaCl aqueous solution; then the organic layer was dried
on anhydrous sodium sulfate and concentrated; the
crude residue was purified by silica gel chromatography
with toluene/EtOAc with gradually increasing polarity.
Pure products 11, 5 were isolated, 6 and 7 separated as
a mixture, which on treatment by the immobilized li-
pase16 Candida antartica in dry EtOAc as acetylating re-
agent, furnished 4-O-acetyl derivative 7c and quite pure
6. Total yield for the coupling between 2 and 3: 78%, 11:
377 mg, 0.35 mmol, 5: 158 mg, 0.25 mmol, 6, 7: 114 mg,
0.18 mmol.
1. Experimental
1.1. General methods
1H and 13C NMR spectra were recorded with an
AVANCE 400 spectrometer (Bruker Biospin); all spec-
tra were run in CDCl3 for derivatives, in D2O for unpro-
tected compounds. Assignments of 1H NMR spectra
were achieved using 2D methods (COSY), 13C NMR
spectra using HMQC and HMBC sequences. Residual
signal of the solvent was used as internal standard:
CHCl3 7.24 ppm, and HOD 4.80 ppm; for 13C NMR,
the central peak CDCl3: 77.0 ppm was taken as refer-
1.4.2. 2.3 equiv of donor 2. Same protocol as before,
except the amount of donor 2. TLC (9:1 toluene/EtOAc)
indicated the presence of two spots with a major one
(Rf 0.14) corresponding to trisaccharide 11 and a fast
running product at Rf 0.36 further identified to tetrasac-
charide 13; TLC (3:2 toluene/EtOAc) shows the pres-

J.-P. Utille, I. Jeacomine / Carbohydrate Research 342 (2007) 2649–2656
2653
0
0
0
0
ence of 5 and small amounts of 6, 7. Total yield for the
coupling: 82%, 13: 0.10 mmol, 11: 0.50 mmol, 5:
0.14 mmol, 6, 7: 0.08 mmol.
5.64 (dd, 1H, H-30, J2 ,3 2.47 Hz, J3 ,4 5.78 Hz), 5.53
(br d, 1H, H-20, J1 ,2 <0.5 Hz), 5.43 (d, 1H, H-10),
5.26, 5.06 (m, 2H, CH2@CH–), 5.01 (d, 1H, H-1, J1,2
0
0
3.61 Hz), 4.76 (dd, 1H, H-50a, J4 ,5 a 3.40 Hz, J5 a,5 b
0
0
0
0
1.5. Allyl 2,3,5-tri-O-benzoyl-a-L-arabinofuranosyl-
(1!3)-a-D-xylopyranoside (5)
10.90 Hz), 4.64 (m, 1H, H-40), 4.61 (dd, 1H, H-50b,
0
0
J4 ,5 b 5.35 Hz), 4.18 (m, 1H, CH2@CH–CH2O–), 3.98
(t, 1H, H-3, J2,3 = J3,4 9.10 Hz), 3.94 (m, 1H,
CH2@CH–CH2O–), 3.72 (m, 1H, H-4), 3.68 (dd, 1H,
H-5a, J4,5a 5.46 Hz, J5a,5b 10.44 Hz), 3.57 (t, 1H, H-5b,
J4,5b 10.44 Hz), 3.52 (dd, 1H, H-2). 13C NMR
(100 MHz, CDCl3): d 166.2–165.6 (3C, PhCO), 133.8–
128.4 (18C, arom C; 1C, CH2@CH–), 117.5 (1C,
CH2@CH–), 107.9 (C-10), 97.5 (C-1), 83.3 (C-20), 80.3
(C-2), 80.1 (C-40), 77.1 (C-30), 73.2 (C-3), 70.1 (C-4),
68.4 (1C, CH2@CH–CH2O–), 63.6 (C-50), 61.1 (C-5);
ESIMS: m/z 657.3 [M+Na]+.
Product 5 was isolated as a syrup (158 mg, 0.25 mmol);
[a]D +51.6 (c 1.0, CHCl3), Rf 0.53 (3:2, toluene/EtOAc);
1H NMR (400 MHz, CDCl3): d 8.15–7.15 (m, 15H,
arom H), 5.92 (m, 1H, CH2@CH–), 5.67 (dd, 1H, H-
30, J2 ,3 2.93 Hz, J3 ,4 5.86 Hz), 5.58 (dd, 1H, H-20,
0
0
0
0
J1 ,2 0.98 Hz), 5.52 (br s, H10, 1H), 5.30, 5.20 (m, 2H,
CH2@CH–), 4.91 (d, 1H, H-1, J1,2 2.98 Hz), 4.79–4.73
0
0
(m, 2H, H-40, H-50a, J4 ,5 a 3.42 Hz, J4 ,5 b 6.83 Hz,
0
0
0
0
J5 a,5 b 12.0 Hz), 4.62 (dd, 1H, H-50b), 4.22, 4.03 (m,
2H, CH2@CH–CH2O–), 3.77 (dd, 1H, H-5a, J4,5a
5.59 Hz), 3.76 (t, 1H, H-3, J2,3 = J3,4 7.91 Hz), 3.74
(dd, 1H, H-2), 3.70 (m, 1H, H-4), 3.58 (t, 1H, H-5b,
J4,5b = J5a,5b 11.90 Hz); 13C NMR (100 MHz, CDCl3):
d 165.7–165.5 (3C, 3PhCO), 133.8–128.2 (18C, arom
C; 1C, CH2@CH–), 118.1 (1C, CH2@CH–), 107.7 (C-
10), 97.1 (C-1), 84.5 (C-3), 82.8 (C-20), 80.4 (C-40), 77.0
(C-30), 71.2 (C-2), 68.7 (CH2@CH–CH2–O–), 68.4 (C-
4), 63.8 (C-50), 61.8 (C-5); ESIMS: m/z 657.3 [M+Na]+.
0
0
1.8. Allyl 2,3-di-O-(2,3,5-tri-O-benzoyl-a-L-arabinofur-
anosyl)-a-D-xylopyranoside (11)
Amorphous solid; [a]D +33.8 (c 1.0, CHCl3); TLC Rf
0.72 (3:2, toluene/EtOAc), Rf 0.14 in (9:1, toluene/
EtOAc); H NMR (400 MHz, CDCl3): d 7.15–8.15 (m,
1
30H, arom H), 5.77 (m, 1H, CH2@CH–), 5.65 (1s, 2
br d, 3H, H-10, H-20, H-200), 5.61 (1s, 1H, H-100,
J1 ,2 <0.5 Hz), 5.59 (br d, 1H, H-300, J3 4 3.81 Hz),
00 00
00 00
1.6. Allyl 2,3,5-tri-O-benzoyl-a-L-arabinofuranosyl-
(1!4)-a-D-xylopyranoside (6)
5.54 (br d, 1H, H-30, J3 ,4 4.84 Hz), 5.24 (m, 1H,
CH2@CH–), 5.04 (m, 1H, CH2@CH–), 4.99 (d, 1H, H-
0
0
1), 4.80 (dd 1H, H-50a, J4 ,5 a 3.23 Hz), 4.78 (dd, 1H,
0
0
Pure compound 6 was isolated during the preparation of
7c from a mixture of 6 and 7 (see 7c). Amorphous solid;
[a]D +38.5 (c 1.0, CHCl3), Rf 0.19 (3:2, toluene/EtOAc);
1H NMR (400 MHz, CDCl3): d 8.15–7.15 (m, 15H,
arom H), 5.91 (m, 1H, CH2@CH–), 5.57 (dd, 1H, H-
H-500a, J4 ,5 a 4.80 Hz), 4.76 (m, 1H, H-400), 4.66 (dd,
00 00
1H, H-50b, J4 ,5 b 5.98 Hz), 4.62 (m, 1H, H-500b, J4 ,5 b
6.40 Hz), 4.56 (m, 1H, H-40), 4.15 (m, 1H, CH2@CH–
CH2O-), 4.03 (dd, 1H, H-3, J2,3 9.58 Hz, J3,4 8.11 Hz),
3.91 (m, 1H, CH2@CH–CH2O-), 3.80 (dd, 1H, H-2),
3.74 (m, 1H, H-4), 3.72 (dd, 1H, H-5a, J4,5a 3.25 Hz,
J5a,5b 12.10 Hz), 3.58 (t, 1H, H-5b, J4,5b 12.10 Hz); 13C
NMR (100 MHz, CDCl3): d 165.9–165.1 (6C, 6PhCO),
133.4–128.1 (36C, arom C; 1C, CH2@CH–), 117.3 (1C,
CH2@CH–), 107.7 (C-10), 107.6 (C-100), 97.6 (C-1),
82.3, 82.2 (C-200, C-3), 81.8–81.6 (C-20, C-40, C-400),
77.8 (C-30), 77.5 (C-300), 77.3 (C-2), 69.5 (C-4), 68.3
(CH2@CH–CH2O–), 63.9 (C-50, C-500), 61.3 (C-5);
ESIMS: m/z 1101.6 [M+Na]+.
0
0
00 00
30, J2 ,3 1.44 Hz, J3 ,4 4.51 Hz), 5.48 (br d, 1H, H-20,
0
0
0
0
J1 ,2 <0.5 Hz), 5.39 (br s, 1H, H-10), 5.33, 5.29 (m, 2H,
CH2@CH–), 4.85 (d, 1H, H-1, J1,2 3.79 Hz), 4.80 (dd,
0
0
1H, H-50a, J4 ,5 a 3.71 Hz, J5 a,5 b 10.93 Hz), 4.77 (m,
0
0
0
0
1H, H-40), 4.65 (dd, 1H, H-50b, J4 ,5 b 4.26 Hz), 4.22,
4.02 (m, 2H, CH2@CH–CH2O–), 3.84 (t, 1H, H-3,
J2,3 = J3,4 9.20 Hz), 3.77 (dd, 1H, H-5a, J4,5a, 5.23 Hz,
J5a,5b 10.95 Hz), 3.74 (m, 1H, H-4), 3.63 (t, 1H, H-5b,
J4,5b 10.95 Hz), 3.57 (dd, 1H, H-2); 13C NMR
(100 MHz, CDCl3): d 166.2, 165.7, 165.5 (3C, 3PhCO),
133.7–128.2 (18C, arom C; 1C, CH2@CH–), 117.9
(CH2@CH–), 105.3 (C-10), 97.1 (C-1), 82.0 (C-20), 81.4
(C-40), 77.4 (C-30), 76.8 (C-4) 73.3 (C-3), 72.2 (C-2),
68.6 (1C, CH2@CH–CH2O–), 63.6 (C-50), 59.4 (C-5);
ESIMS: m/z 657.3 [M+Na]+.
0
0
1.9. Allyl 2,3,4-tri-O-(2,3,5-tri-O-benzoyl-a-L-arabino-
furanosyl)-a-D-xylopyranoside (13)
Amorphous solid; [a]D +26.63 (c 1.0, CHCl3); TLC Rf
0.36 (9:1, toluene/EtOAc); 13C NMR (100 MHz,
CDCl3): d 166.1–165.1 (9C, 9PhCO), 133.5–128.1 (54C,
arom C; 1C, CH2@CH–), 117.1 (1C, CH2@CH–),
107.6, 106.1, 105.8 (C-10, C-100, C-1000, Ara), 97.7 (C-1,
Xyl), 82.3, 82.2, 081.9, 81.7, 81.5, 81.4, 80.8, 78.2, 77.4,
77.0 (10 C, C-2 , C-200, C-2000, C-3, C-30, C-300, C-3000,
C-40, C-400, C-4000), 74.2, 73.8 (C-2, C-4), 68.4 (1C,
1.7. Allyl 2,3,5-tri-O-benzoyl-a-L-arabinofuranosyl-
(1!2)-a-D-xylopyranoside (7)
Amorphous solid; [a]D +50.2 (c 1.0, CHCl3); Rf 0.19
1
(3:2, toluene/EtOAc); H NMR (400 MHz, CDCl3): d
8.15–7.15 (m, 15H, arom H), 5.83 (m, 1H, CH2@CH–),

2654
J.-P. Utille, I. Jeacomine / Carbohydrate Research 342 (2007) 2649–2656
CH2@CH–CH2–O–), 64.0, 63.7, 63.5 (C-50, C-500, C-5000),
59.7 (C-5, Xyl); ESIMS: m/z 1546.0 [M+Na]+.
118.1 (1C, CH2@CH–), 105.2 (C-10), 101.3 (C-1), 82.0
(C-20), 81.7 (C-40), 77.5 (C-30), 76.1 (C-4), 72.5 (C-3),
71.6 (C-2), 69.7 (CH2@CH–CH2O–), 63.6 (C-50), 61.21
(C-5); ESIMS: m/z 657.3 [M+Na]+.
1.10. Coupling reactions: with allyl b-D-xylopyranoside
4 as acceptor
1.13. Allyl 2,3,5-tri-O-benzoyl-a-L-arabinofuranosyl-
(1!2)-b-D-xylopyranoside (10)
1.10.1. 1.5 equiv of donor 2. Same conditions as de-
scribed for 3; 1 mmol of acceptor 4, total yield 72%,
12: 0.07 mmol, 8: 0.43 mmol, 9: 0.14 mmol, 10:
0.08 mmol.
Amorphous solid; [a]D ꢁ7.5 (c 1.0, CHCl3); TLC Rf 0.18
1
(3:2, toluene/EtOAc); H NMR (400 MHz, CDCl3): d
8.15–7.15 (m, 15H, arom H), 5.83 (m, 1H, CH2@CH–),
5.62 (br d, 1H, H-30, J2 ,3 1.60 Hz, J3 ,4 5.27 Hz),
0
0
0
0
1.10.2. 2.3 equiv of donor 2. 1 mmol of acceptor 4,
total yield 82%; 12: 0.49 mmol, 8: 0.10 mmol, 9:
0.12 mmol, 10: 0.11 mmol.
5.57 (s, 1H, H-10, J1 ,2 <1 Hz), 5.49 (br d, 1H, H-20),
5.24, 5.08 (m, 2H, CH2@CH–), 4.78 (dd, 1H, H-50a,
0
0
J4 ,5 a 3.27 Hz, J5 a,5 b 11.46 Hz), 4.72 (m, 1H, H-40,
0
0
0
0
J4 ,5 b 4.53 Hz), 4.66 (dd, 1H, H-50b), 4.61 (d, 1H, H-1,
J1,2 5.63 Hz), 4.25 (m, 1H, CH2@CH–CH2O–), 4.04
(dd, 1H, H-5a, J4,5a 4.14 Hz, J5a,5b 11.80 Hz), 3.95 (m,
1H, CH2@CH–CH2O–), 3.78 (t, 1H, H-3, J2,3 = J3,4
7.11 Hz), 3.70 (dd, 2H, H-2, H-4, J4,5a 4.14 Hz, J4,5b
7.38 Hz), 3.38 (dd, 1H, H-5b); 13C NMR (100 MHz,
CDCl3): d 166.1–165.7 (3C, PhCO), 133.7–128.3 (18C,
arom C; 1C, CH2@CH–), 117.7 (1C, CH2@CH–),
106.3 (C-10), 100.1 (C-1), 83.0 (C-20), 80.8 (C-40), 77.7
(C-30), 76.7 (C-2), 75.7 (C-3), 69.8 (1C, CH2@CH–
CH2O–), 69.7 (C-4), 63.8 (C-5), 63.6 (C-50); ESIMS:
m/z 657.3 [M+Na]+.
0
0
1.11. Allyl 2,3,5-tri-O-benzoyl-a-L-arabinofuranosyl-
(1!3)-b-D-xylopyranoside (8)
Amorphous solid; [a]D ꢁ1.9 (c 1.0, CHCl3); TLC Rf 0.48
1
(3:2, toluene/EtOAc); H NMR (400 MHz, CDCl3): d
8.15–7.15 (m, 15H, arom H), 5.93 (m, 1H, CH2@CH–),
5.66 (dd, 1H, H-30, J2 ,3 2.65 Hz, J3 ,4 5.50 Hz), 5.57
0
0
0
0
(dd, 1H, H-20, J1 ,2 1.15 Hz), 5.50 (br s, 1H, H10), 5.49
(dd, 1H, H-50a, J4 ,5 a 3.60 Hz, J5 a,5 b 12.80 Hz), 5.48
0
0
0
0
0
0
(m, 1H, H-40, J4 ,5 b 6.67 Hz), 5.35–5.18 (m, 2H,
CH2@CH–), 4.61 (dd, 1H, H-50b), 4.34 (m, 1H,
CH2@CH–CH2–O–), 4.32 (d, 1H, H-1, J1,2 7.43 Hz),
4.13 (m, 1H, CH2@CH–CH2–O–), 4.05 (dd, 1H, H-5a,
J4,5a 5.52 Hz, J5a,5b 11.70 Hz), 3.74 (m, 1H, H-4, J4,5b
10.16 Hz), 3.59 (dd, 1H, H-2, J2,3 8.72 Hz), 3.50 (t,
1H, H-3, J3,4 8.72 Hz), 3.23 (dd, 1H, H-5b); 13C NMR
0
0
1.14. Allyl 2,3-di-O-(2,3,5-tri-O-benzoyl-a-L-arabinofur-
anosyl)-b-D-xylopyranoside (12)
(100 MHz, CDCl3):
d
166.1–165.6 (3C, 3PhCO),
Amorphous solid; [a]D +3.9 (c 1, CHCl3); TLC Rf 0.52
1
133.8–128.4 (18C, arom C; 1C, CH2@CH–), 117.9 (1C,
CH2@CH–), 107.9 (C-10), 102.2 (C-1), 86.7 (C-3), 82.9
(C-20), 80.6 (C-40), 77.0 (C-30), 72.7 (C-2), 70.0
(CH2@CH–CH2O–), 68.5 (C-4), 65.3 (C-5), 63.6 (C-
50); ESIMS: m/z 657.3 [M+Na]+.
(7:3, toluene/EtOAc); H NMR (400 MHz, CDCl3): d
8.15–7.15 (m, 30H, arom H), 5.88 (s, 1H, H-10,
0
0
J1 ,2 <1 Hz), 5.73 (m, 1H, CH2@CH–), 5.63 (br d,
1H, H-20, J2 ,3 0.85 Hz), 5.61 (br s, 1H, H-100,
0
0
J1 ,2 <1 Hz), 5.58 (br d 1H, H-300, J2 ,3 0.75 Hz, J3 ,4
00 00
00 00
00 00
4.08 Hz), 5.57 (br d, 1H, H-200), 5.52 (br d, 1H, H-30,
0
0
1.12. Allyl 2,3,5-tri-O-benzoyl-a-L-arabinofuranosyl-
(1!4)-b-D-xylopyranoside (9)
J3 ,4 4.56 Hz), 5.10–4.94 (m, 2H, CH2@CH–), 4.88
(m, 1H, H-40), 4.82 (dd, 1H, H-50a, J4 ,5 a 3.02 Hz,
0
0
J5 a,5 b 11.98 Hz), 4.78 (dd, 1H, H-500a, J4 ,5 a 3.73 Hz,
0
0
00 00
J5 a,5 b 13.02 Hz), 4.76 (m, 1H, H-400), 4.68 (dd, 1H,
00
00
Amorphous solid; [a]D ꢁ22.5 (c 1.0, CHCl3); TLC Rf
0.31 (3:2, toluene/EtOAc); 1H NMR (400 MHz,
CDCl3): d 8.15–7.15 (m, 15H, arom H), 5.85 (m,
H-50b, J4 ,5 b 4.61 Hz, J5 a,5 b 11.96 Hz), 4.63 (dd, 1H,
0
0
0
0
H-500b, J4 ,5 b 7.44 Hz), 4.39 (d, 1H, H-1, J1,2
00 00
CH2@CH–), 5.57 (br d,1H, H-30, J2 ,3 1.20 Hz, J3 ,4
7.55 Hz), 4.27 (m, 1H, CH2@CH–CH2O–), 4.07 (dd,
1H, H-5a, J4,5a 4.87 Hz, J5a,5b 11.75 Hz), 3.91 (dd,
1H, H-2, J2,3 8.90 Hz), 3.87 (m, 1H, CH2@CH–
CH2O), 3.76 (m, 1H, H-4), 3.74 (t, 1H, H-3), 3.27
(dd, 1H, H-5b, J4,5b 9.40 Hz); 13C NMR (100 MHz,
CDCl3): d 166.3–165.2 (6C, PhCO), 133.7–128.2 (36
C, arom C; 1C, CH2@CH–), 117.9 (1C, CH2@CH–),
107.9 (C-100), 105.8 (C-10), 101.2 (C-1), 88.1 (C-3),
82.2 (C-400), 82.0 (C-20), 81.7 (C-40), 81.6 (C-200), 78.1
(C-30), 77.1 (C-300), 74.6 (C-2), 70.1 (1C, CH2@CH–
CH2O–), 69.3 (C-4), 65.3 (C-5), 63.9 (C-50), 63.8 (C-
500); ESIMS: m/z 1101.5 [M+Na]+.
0
0
0
0
4.30 Hz), 5.51 (br d, 1H, H-20, J1 ,2 <1 Hz), 5.41
(s, 1H, H-10), 5.17–5.13 (m, 2H, CH2@CH–), 4.80 (dd,
0
0
1H, H-50a, J4 ,5 a 3.20 Hz, J5 a,5 b 11.36 Hz), 4.74 (m,
0
0
0
0
1H, H-40, J4 ,5 b 4.73 Hz), 4.65 (dd, 1H, H-50b), 4.52
(d, 1H, H-1, J1,2 5.33 Hz), 4.30 (m, 1H, CH2@CH–
CH2O–), 4.09 (dd, 1H, H-5a, J4,5a 3.73 Hz, J5a,5b
11.33 Hz), 4.07 (m, 1H, CH2@CH–CH2O–), 3.82 (m,
1H, H-4, J4,5b 7.20 Hz), 3.79 (br t, 1H, H-3, J2,3 = J3,4
7.11 Hz), 3.52 (br dd, 1H, H-2), 3.50 (dd, 1H, H-5b);
13C NMR (100 MHz, CDCl3): d 165.7–165.4 (3C,
PhCO), 133.6–128.3 (18C, arom C; 1C, CH2@CH–),
0
0

J.-P. Utille, I. Jeacomine / Carbohydrate Research 342 (2007) 2649–2656
2655
1.15. b-D-Xylopyranosyl-(1!4)-1,2,3-tri-O-acetyl-a-D-
Acknowledgements
xylopyranose (15)
The authors, thank Dr. C. Bosso for assistance with
mass spectrometry, Dr. H. Driguez and Dr. S. Halila
for helpful discussions.
To a solution of 1,2,3,20,30-penta-O-acetyl-a-xylobiose18
14 (443 mg, 0.9 mmol) in DCM/MeOH (9:1; 10 mL) was
added dry K2CO3 (187 mg, excess 1.5/1), the mixture
was stirred at rt for 2 h; additional K2CO3 (125 mg,
0.9 mmol) was added and stirring continued for 2 h.
The solution was filtered and concentrated in vacuo;
the residue was chromatographed on silica gel and prod-
uct 15 isolated: 50% yield, amorphous solid; [a]D +17.3
(c 1, CHCl3); TLC Rf 0.27 (3:2, EtOAc/acetone); se-
Supplementary data
Supplementary data associated with this article can be
found, in the online version, at doi:10.1016/j.carres.
2007.08.007.
1
lected data, H NMR (400 MHz, CDCl3): d 6.11(d, H-
1, J1,2 3.62 Hz), 5.25 (t, H-3, J2,3 = J3,4 9.5 Hz), 4.89
(dd, H-2), 4.21 (d, H-10, 6.1 Hz), 3.85–3.12 (m, 8H, H-
4, H-5a,b, H-20, H-30, H-40, H-50a,b); 13C NMR
(100 MHz, CDCl3): d 170.7, 169.8, 169.1 (CH3CO),
102.4 (C-10), 89.1 (C-1), 75.8, 74.6, 72.7, 70.1, 69.4,
69.2 (C-2, C-20, C-3, C-30, C-4, C-40), 65.3 (C-50), 61.3
(C-5), 20.8–20.3 (3s, CH3CO).
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000 000
´
´
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00 00
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J4 ,5 a 3.70 Hz, J5 a,5 b 12.20 Hz), 4.90 (dd, 1H, H-2),
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´
Remond, C.; Ferchichi, M.; Aubry, N.; Plantier-Royon,
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R.; Portella, C.; O’ Donohue, M. J. Tetrahedron Lett.
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3.72 (m, 1H, H-40), 3.70 (t, 1H, H-30, J3 ,4 8.10 Hz),
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0
0
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50b, J4 ,5 b 8.85 Hz), 2.03, 1.99, 1.96 (3s, CH3CO); 13C
NMR (100 MHz, CDCl3): d 169.9, 169.8, 169.1 (3C,
CH3CO), 166.3, 166.1, 165.8, 165.6, 165.6, 165.1 (6C,
6PhCO), 133.6–128.3 (36C, arom C), 107.8 [C-1000;
Ara-(1!3)-linked], 106.7 [C-100; Ara-(1!2)-linked],
101.3 (C-10, Xyl), 89.1 (C-1, Xyl), 87.3 (C-30), 82.3 (C-
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77.2 (C-3000), 76.1 (C-20), 74.1 (C-4), 69.9 (C-3), 69.3
(C-2, C-40), 65.2 (C-50), 63.9, 63.8 (C-500, C-5000), 61.4
(C-5), 20.9, 20.6, 20.5 (CH3CO); ESIMS m/z 1319.6
[M+Na]+.
0
0
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