Synthesis of an O-sulfo LewisX analog as glycolipid antigen

Article abstract of DOI:10.1016/j.carres.2011.06.027

The title compound containing dihydroceramide as a ligand for CD1d was accomplished using the mannosyl, glucosaminyl, and fucosyl donors, and a sphinganine analogue, as suitable building blocks. The 2-O-unprotected mannosyl donor was coupled effectively w

Full text of DOI:10.1016/j.carres.2011.06.027

Carbohydrate Research 346 (2011) 2091–2097
Contents lists available at ScienceDirect
Carbohydrate Research
journal homepage: www.elsevier.com/locate/carres
Synthesis of an O-sulfo LewisX analog as glycolipid antigen
⇑
Shuhei Ueno, Shigeomi Horito
Department of Biological Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 2 May 2011
Received in revised form 4 June 2011
Accepted 21 June 2011
Available online 29 June 2011
The title compound containing dihydroceramide as a ligand for CD1d was accomplished using the man-
nosyl, glucosaminyl, and fucosyl donors, and a sphinganine analogue, as suitable building blocks. The 2-
O-unprotected mannosyl donor was coupled effectively with the sphinganine analog to afford the mann-
nosyl sphinganine derivative. The coupling of the glucosaminyl donor with the mannnosyl sphinganine
acceptor required triflic acid as a promoter and the promoter change to silver triflate led to the undesired
glycal production. The reduction of azide group using Zn powder was the key process, in which the
amount of acetic acid was restricted to avoid the benzoyl migration and N-trichloroacetyl deprotection.
The trisaccharide glycolipid was sulfonated at the 3-position of fucose moiety.
Keywords:
Glycolipid antigen
O-Sulfo LewisX
Sphinganine
CD1d ligand
Ó 2011 Elsevier Ltd. All rights reserved.
1. Introduction
lipid-immunized antibody production against glycoproteins is a
challenging study because glycolipids are much readily obtainable
Cancer-associated glycoproteins and glycolipids have been
found by characterization of cancers.1–4 These cancer-cell glycans
were associated with malignant transformation, hematogenous
metastasis and angiogenesis.5 Levels of fucosyl-, b-galactosyl-, b-
N-acetylgalactosaminyl-, sialyl-, and sulfotransferase activities of
various cancer cell lines were examined and the existence of un-
ique carbohydrate moieties in cancer-associated glycolipids was
predicted.6 Whereas, the CD1 family of antigen presenting glyco-
proteins has been well studied7 and the crystal structure of CD1d
revealed that two deep hydrophobic pockets were able to accom-
modate two hydrocarbon chains.8
than glycoproteins.
2. Results and discussion
Three sugar and one lipid components were required for a
chemical synthesis of target compound 1. A saturated sphinganine
analog was selected as the ligand for CD1d because of synthetic
process truncation. Therefore, known sphingosine analog 29 was
hydrogenated using H2 and Pd/C to afford saturated lipid
component 3 (92%) as depicted in Scheme 1.
The glucosaminyl donor was prepared in the following way
(Scheme 2). Glucosamine derivative 410 was protected by a
p-methoxybenzyl (MB) group to afford 5 in 76% yield. The benzyl-
idene group of 5 was hydrolyzed in 90% aqueous acetic acid,
followed by benzylation, to provide glucosaminyl donor 6 in a
72% yield over two steps.
The fucosyl donor was obtained in the following manner
(Scheme 3). Isopropylidenation of known thiofucoside 711 afforded
8 (65%), of which the protection with an allyl group afforded 9
(90%). The isopropylidene group of 9 was hydrolyzed in 90%
aqueous acetic acid to yield deprotected compound 10 (90%). Par-
tial protection of 10 using dibutyltin oxide and p-methoxybenzyl
HO
O
HO
O
O
AcHN
O
HO
OH
O
HO
OSO3Na
HO
OH
(CH2)16CH3
(CH2)16CH3
HO
O
HN
1
O
In these contexts, target molecule 1 as a cancer antigen
candidate was designed to mimic a partial structure of LewisX,
which can be constructed by the cancer specific activation of
corresponding transferases in N-glycan biosynthesis. A glyco-
OH OBz
N3
OH OBz
H2, Pd/C, MeOH
92%
(CH2)14CH3
(CH2)14CH3
N3
2
3
⇑
Corresponding author. Tel.: +81 4 7124 1501; fax: +81 4 7125 1841.
E-mail address: shorito@rs.noda.tus.ac.jp (S. Horito).
Scheme 1.
0008-6215/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carres.2011.06.027

2092
S. Ueno, S. Horito / Carbohydrate Research 346 (2011) 2091–2097
p-methoxybenzyl group of 14 was deprotected using ammonium
cerium(IV) nitrate (CAN) to yield acceptor 15 (72%). Condenzation
of 15 and fucosyl donor 11 under NIS–TfOH promotion afforded tri-
Ph
Ph
O
BnO
BnO
MBO
O
O
O
O
O
O
a
b, c
SPh
NHTCA
SPh
NHTCA
SPh
NHTCA
HO
MBO
4
5
6
saccharide 16 (67%), of which newly constructed
a-configuration
was confirmed by 1H NMR spectroscopy (J1,2 = 3.4 Hz).
Scheme 2. Reagents and conditions: (a) NaH, MBCl, DMF, 0 °C, 76%; (b) 90% HOAc;
(c) NaH, BnBr, DMF, 0 °C, 72% (two steps).
Deprotected compound 17 (63%) was prepared by PdCl2-catal-
ized deallylation of 16 and again protected by benzoyl group to af-
ford benzoate 18 in a 92% yield. We attempted to carry out
trichloroacetyl (TCA) and azido group reduction using tributyltin
hydride; however, benzoyl migration to the newly produced amino
group was inevitable. The problem was resolved by an unexpected
reaction. Azido group reduction of 18 was accomplished using Zn
powder without the removal of the N-trichloroacetyl group in spite
of its removal conditions. Ratios of HOAc and CH2Cl2 were critical
during the treatment with zinc: azide group reduction and de-N-
trichloroacetylation were normally observed in a high concentra-
tion (0.06:1 HOAc–CH2Cl2) to afford derivative 20 (60%); the de-
N-trichloroacetylation was prevented in a middle concentration
(0.05:1 HOAc–CH2Cl2) to afford desired compound 19 (61%); start-
ing material 18 was completely recovered in a low concentration
(0.02:1 HOAc–CH2Cl2). Subsequent coupling of the amino group
of 19 with octadecanoic acid using N-(3-dimethylaminopropyl)-
N0-ethylcarbodiimide hydrochloride (WSC) afforded glycolipid
derivative 21 (55% two steps) and the trichloroacetyl group was
converted to acetyl group by radical reduction using tributyltin hy-
dride to yield 22 (98%).
The p-methoxybenzyl group of 22 was deprotected using CAN
to afford 23 (69%), which was sulfonated using sulfur trioxide–pyr-
idine complex to yield 24 (79%). Removal of the benzyl group with
sodium bromate and sodium dithionite afforded 25 in a 33%
yield.14 The removal of acyl groups with NaOMe in MeOH gave 1
in an 86% yield. The formation of 3-O-sulfonated derivatives was
proven by 1H NMR spectroscopy. The 33-protons of the sulfonated
24 and 25 showed the remarkable down-field shifts of 1.29–
1.45 ppm compared with that of the non-sulfonated 23. Moreover,
the sulfonated 33-proton of 1 also showed the down-field shifts of
0.50 and 0.42 ppm compared with the non-sulfonated 23- and 43-
SPh
SPh
SPh
O
7
O
O
a
c
b
OH
OH
OAll
OH
OH
O
O
HO
HO
O
O
8
9
SPh
OAll
SPh
OAll
O
10
O
e, d
OMB
AcO
11
Scheme 3. Reagents and conditions: (a) 2-methoxy propene, p-toluenesulfonic
acid, acetone, 65%; (b)AllBr, NaH, DMF, 0 °C, 90%; (c) 90% HOAc, 60 °C, 90%; (d)
Bu2SnO, TBAI, NaH, MBCl, 120 °C; (e) Ac2O, pyridine, 60% (two steps).
chloride and ensuing acetylation furnished the fucosyl donor 11
(60%).
The construction of the target compound 1 is outlined in
Scheme 4. Condensation of sphinganine acceptor 3 with mannno-
syl donor 1212 having a hydroxyl group at C-2, which was designed
in this research as a donor with moderate activity afforded
nopyranoside 13 (75%), of which the -configuration was ascer-
a-man-
a
tained by 13C NMR spectroscopy (JC-1,H-1 = 173 Hz).13 Although it
might be expected that 2-O-chloroacetylated 12 would improve a
condensation yield, a similar mannosylation using 2-O-chloroacet-
ylated 12 never afforded the desired product because the conden-
sation was preceded by acyl migration of the 2-O-chloroacetyl
group to the acceptor. A second condensation of acceptor 13 with
glucosaminyl donor 7 under NIS–TfOH promotion yielded disac-
charide 14, of which the newly constructed b-configuration was
confirmed by 1H NMR spectroscopy (J1,2 = 7.9 Hz). Glycal produc-
tion was promoted by use of silver triflate instead of triflic acid
as the promoter and no desired product was generated. The
BnO
BnO
O
O
OH
O
BzO
BzO
BzO
BnO
BnO
O
O
MBO
HO
b
c
TCAHN
BzO
TCAHN
BzO
R
O
O
BzO
BzO
12 R = SPh
13 R = OEN3
BzO
BzO
a
14
15
OEN3
AcO
OEN3
i
BnO
BnO
BnO
O
O
O
BnO
O
O
O
TCAHN
BzO
R2HN
g
O
O
d
BzO
OR
OBz
BzO
BzO
O
O
h
BzO
OMB
OMB
AcO
BzO
OR1
19 R1 = ENH2, R2=TCA
OEN3
16
17
R = All
R = H
18 R = Bz
e
f
1
2
20
R = ENH2, R =H
21 R1 = Eod, R2=TCA
BnO
O
BnO
O
O
HO
HO
AcHN
BzO
O
O
m
O
l
OBz
O
O
1
BzO
OR
AcHN
BzO
AcO
O
BzO
OBz
O
BzO
EodO
k
22
23
24
OSO3H
R = MB
R = H
R = SO3HNEt3
AcO
j
BzO
OEod
25
OBz
OBz
OBz
Eod =
(CH2)16CH3
(CH2)16CH3
(CH2)16CH3
EN3 =
ENH2
=
(CH2)16CH3
HN
NH2
N3
O
Scheme 4. Reagents and conditions: (a) 3, NIS, AgOTf, MS 4 Å, CH2Cl2, 0 °C, 75%; (b) 6, NIS, HOTf, MS 4 Å, CH2Cl2, ꢀ15 °C; 70%; (c) CAN, 10:1 CH3CN/H2O, 72%; (d) 11, NIS,
HOTf, MS 4 Å, CH2Cl2, 0 °C, 67%; (e) PdCl2, 2:1 MeOH/CH2Cl2, 63%; (f) BzCl, Pyr, CH2Cl2, 92%; (g) Zn, HOAc, CH2Cl2, 0 °C, 61%; (h) octadecanoic acid, WSC, CH2Cl2, 75%; (i)
Bu3SnH, DMA, AIBN, C6H6, 120 °C, 98%; (j) CAN, 10:1 CH3CN/H2O, 69%; (k) SO3/pyridine, DMF, 79%; (l) NaBrO3, Na2S2O4, 1:2 AcOEt/H2O, 33%; (m) NaOMe, MeOH, H2O, 86%.

S. Ueno, S. Horito / Carbohydrate Research 346 (2011) 2091–2097
2093
protons, respectively. The desired antigen 1 was obtained, which
will be applied to an immunization study.
coevaporated with toluene. The residue was dissolved in DMF
(19 mL) and added NaH (0.680 g, 14.0 mmol) at 0 °C. The mixture
was stirred at 0 °C for 30 min before benzyl bromide (1.66 mL,
14.0 mmol) was added. Stirring was continued at 0 °C for 1 h.
The processing of the mixture was performed, as described for 5,
which was then purified using flash chromatography (1:5 EtOAc–
3. Experimental
3.1. General methods
hexane) to afford 6 (1.63 g, 72% yield of 2 steps). [
a
]
D
+0.1 (c
1.00, CHCl3); 1H NMR (CDCl3): d 7.56–7.14 (m, 19H, 3Ph, p-
MeOC6H4), 6.88 (d, 1H, JNH,2 = 7.2 Hz, NH), 5.12 (d, 1H,
J1,2 = 9.8 Hz, H-1), 4.79 (d, 1H, CH2Ph), 4.72 (d, 1H, CH2Ph), 4.64–
4.59 (m, 3H, 3CH2Ph), 4.56 (d, 1H, CH2Ph), 4.07 (dd, 1H,
J2,3 = J3,4 = 9.4 Hz, H-3), 3.81 (dd, 1H, H-6a), 3.79–3.75 (m, 4H, H-
6b, OCH3), 3.66–3.61 (m, 2H, J4,5 = 9.6 Hz, H-4, H-5), 3.58 (m, 1H,
H-2); 13C NMR (CDCl3): d 137.1, 133.5, 132.9, 129.2, 128.3, 126.0,
113.9, 113.5, 111.0, 85.2 (C-1), 81.8 (C-3), 79.2 (C-4), 74.7 (CH2Ph),
74.0 (CH2Ph), 73.9 (CH2Ph), 69.9 (C-5), 68.6 (C-6), 55.3 (C-2). Anal.
Calcd for C36H36Cl3NO6S: C, 60.30; H, 5.06; N, 1.95; S, 4.47. Found:
C, 60.42; H, 4.90; N, 1.68; S, 4.23.
The optical rotations were measured at 25 °C using a JASCO DIP-
370 polarimeter. The 1H NMR and 13C NMR spectra were recorded
on a Bruker DRX-600 spectrometer at 600 and 125 MHz, respec-
tively. The dH-value in CDCl3 is relative to internal Me4Si and the
dC-value is referenced to the solvent [dC (CDCl3) 77.0]. The assign-
ments were aided by COSY, TOCSY and 1H–13C correlation spec-
troscopy. ‘E’ designates signals belonging to the eicosanediol, ‘A’
is used for signals stemming from the octadecanamide. Elemental
analyses were performed on a Parkin–Elmer 2400 II elemental ana-
lyzer. All reactions were monitored using TLC with aluminum
sheets that were coated with Silica Gel 60F254 (0.2 mm thickness,
E. Merck, Darmstadt, Germany). Column chromatography was con-
ducted using Wako gel C-300E (Wako). All reactions were carried
out under argon atmosphere with dried solvent. Solvent extracts
were dried with anhydrous MgSO4.
3.5. Phenyl 3,4-O-isopropylidene-1-thio-b-L-fucopyranoside (8)
To a solution of 710 (1.84 g, 7.19 mmol) in acetone (37 mL) and
2-methoxy propene (1.20 mL, 14.4 mmol) was added p-toluenesul-
fonic acid (270 mg, 1.44 mmol) at 0 °C. The mixture was stirred at
rt for 3 h. The reaction was quenched by the addition of Na2CO3
and filtered through a pad of Celite. The filtrate was concentrated
and purified using flash chromatography (1:4 EtOAc–hexane) to af-
3.2. (2S,3R)-2-Azido-3-O-benzoyl-1,3-eicosanediol (3)
To a solution of 28 (560 mg, 806
lmol) in MeOH (28 mL) was
added Pd/C (268 mg) and the mixture was stirred at hydrogen atmo-
sphere for 3 h. The catalyst was filtered off and concentrated to af-
ford 8 (1.33 g, 65%). [
a]
ꢀ0.5 (c 1.0, CHCl3); 1H NMR(CDCl3): d
D
7.58–7.28 (m, 5H, Ph), 4.42 (d, 1H, J1,2 = 10.2 Hz, H-1), 4.06 (dd,
1H, J3,4 = 5.0 Hz, J4,5 = 1.8 Hz, H-4), 4.04 (dd, 1H, J2,3 = 2.2 Hz, H-3),
3.89 (ddd, 1H, J5,6 = 6.5 Hz, H-5), 3.54 (ddd, 1H, H-2), 2.45 (d, 1H,
OH), 1.44 (d, 3H, H-6), 1.43 (s, 3H, OCCH3), 1.35 (s, 3H, OCCH3);
13C NMR (CDCl3): d 134.6, 131.5, 130.5, 129.3, 128.7, 87.7 (C-1),
78.8 (C-3), 76.2 (C-4), 72.7 (C-5), 71.2 (C-2), 28.1, 26.3 (2COCH3),
17.0 (C-6). Anal. Calcd for C15H20O4S: C, 60.79; H, 6.80; S, 10.82.
Found: C, 60.51; H, 6.96; S, 11.11.
ford 3 (385 mg, 92%) as a colorless syrup. [
a
]
D ꢀ10.4 (c 1.0, CHCl3);
1H NMR (CDCl3): d 8.08–7.42 (m, 5H, Ph), 5.28 (m, 1H, H-3), 3.83
(dd, 1H, H-1a), 3.72–3.67 (m, 2H, H-1b, H-2), 1.84 (m, 1H, H-4a),
1.75 (m, 1H, H-4b), 1.46–1.18 (m, 30H, 15CH2), 0.88 (t, 3H, CH2CH3);
13C NMR (CDCl3): d 166.3, 133.4, 129.8, 128.5, 73.2 (C-3), 65.8 (C-2),
61.8 (C-1), 31.9, 30.4 (C-4), 29.6, 29.6, 29.6, 29.5, 29.5, 29.4, 29.3,
25.2, 22.7, 14.1 (CH2CH3). Anal. Calcd for C27H45N3O3: C, 70.55; H,
9.87; N, 9.14. Found: C, 70.68; H, 10.09; 8.86.
3.6. Phenyl 2-O-allyl-3,4-O-isopropylidene-1-thio-b-L-
fucopyranoside (9)
3.3. Phenyl 4,6-O-benzylidene-2-deoxy-3-O-p-methoxybenzyl-
1-thio-2-trichloroacetamide-b-D-glucopyranoside (5)
To a solution of 410 (2.46 g, 4.87 mmol) in DMF (16 mL) was
added NaH (0.470 g, 9.74 mmol) at 0 °C. The mixture was stirred
at 0 °C for 15 min before p-methoxybenzyl chloride (1.30 mL,
9.59 mmol) was added. Stirring was continued at 0 °C for 1 h.
The reaction mixture was quenched by the addition of ice, ex-
tracted with CH2Cl2. The organic phase was washed with saturated
aqueous NaHCO3 and brine, dried, concentrated in vacuo, and co-
evaporated with toluene. The residue was purified using flash
chromatography (1:4.5 EtOAc–hexane) to afford 5 (2.31 g, 76%).
To a solution of 8 (1.33 g, 4.68 mmol) in DMF (8.0 mL) was
added NaH (940 mg, 23.4 mmol) at 0 °C. The mixture was stirred
at rt for 1 h before allyl bromide (1.2 mL, 14.0 mmol) was added
at 0 °C. Stirring was continued at rt for 1 h. The processing of the
reaction was performed, as described 5, which was purified using
flash chromatography (1:3 EtOAc–hexane) to afford 9 (1.42 g,
90%). [a]
+6.8 (c 1.0, CHCl3); 1H NMR(CDCl3): d 7.56–7.23 (m,
D
5H, Ph), 5.97–5.90 (m, 1H, CHCH2), 5.30–5.26 (m, 1H, CHCH2),
5.19–5.16 (m, 1H, CHCH2), 4.54 (d, 1H, J1,2 = 9.8 Hz, H-1), 4.30–
4.26 (m, 1H, OCH2CHCH2), 4.17–4.12 (m, 1H, OCH2CHCH2), 4.17–
4.12 (m, 1H, H-3), 4.04 (dd, 1H, J4,5 = 1.8 Hz, H-4), 3.82 (ddd, 1H,
J5,6 = 6.5 Hz, H-5), 3.42 (dd, 1H, H-2), 1.47 (s, 3H, OCCH3), 1.40 (d,
3H, H-6), 1.35 (s, 3H, OCCH3); 13C NMR (CDCl3): d 134.6, 131.5,
130.5, 129.3, 128.7, 135.3 (OCH2CHCH2), 117.7 (OCH2CHCH2),
86.2 (C-1), 79.9 (C-3), 77.6 (C-2), 76.6 (C-4), 72.4 (C-5), 72.3
(OCH2CHCH2), 27.9, 26.3 (2OCCH3), 16.9 (C-6). Anal. Calcd for
[
a]
D
ꢀ8.6 (c, CHCl3); 1H NMR (CDCl3): d 7.53–6.79 (m, 14H, 2Ph,
p-MeOC6H4), 6.85 (d, 1H, JNH,2 = 7.2 Hz, NH), 5.60 (s, 1H, CHPh),
5.27 (d, 1H, J1,2 = 10.4 Hz, H-1), 4.81 (d, 1H, CH2Ph), 4.61 (d, 1H,
CH2Ph), 4.42 (dd, 1H, J5,6a = 4.9 Hz, J6a,6b = 11.2 Hz, H-6a), 4.23 (t,
1H, J2,3 = 9.2 Hz, J3,4 = 9.4 Hz, H-3), 3.82 (t, 1H, J5,6b = 10.2 Hz, H-
6b), 3.77 (s, 3H, OCH3), 3.68 (t, 1H, J4,5 = 9.6 Hz, H-4), 3.60 (m,
1H, H-5), 3.49 (m, 1H, H-2); 13C NMR (CDCl3): d 137.1, 133.5,
129.2, 128.3, 126.0, 123.8, 117.1, 113.9, 113.5, 111.0, 101.3 (CHPH),
85.2 (C-1), 82.5 (C-3), 76.7 (C-4), 74.6 (CH2PH), 70.4 (C-5), 68.6 (C-
6), 57.3 (C-2). Anal. Calcd for C29H28Cl3NO6S: C, 55.73; H, 4.52; N,
2.24; S, 5.13. Found: C, 55.64; H, 4.24; N, 2.23; S, 5.27.
C18H24O4S: C, 64.26; H, 7.19; S, 9.53. Found: C, 64.19; H, 7.46; S,
9.55.
3.7. Phenyl 2-O-allyl-1-thio-b-L-fucopyranoside (10)
3.4. Phenyl 4,6-di-O-benzyl-2-deoxy-3-O-p-methoxybenzyl-1-
thio-2-trichloroacetamido-b-D-glucopyranoside (6)
A solution of 9 (1.42 g, 4.22 mmol) in HOAc (26 mL) and water
(2.6 mL) was heated at 60 °C for 2 h. The mixture was co-evapo-
rated with toluene. The residue was purified using flash chroma-
A solution of 5 (2.01 g, 3.23 mmol) in 90% HOAc (36 mL) was
heated at 50 °C for 2.5 h. The mixture was concentrated and
tography (1:1 EtOAc–hexane) to afford 10 (1.13 g, 90%). [
a]
D
+19.0 (c 1.0, CHCl3); 1H NMR (CDCl3): d 7.56–7.25 (m, 5H, Ph)

2094
S. Ueno, S. Horito / Carbohydrate Research 346 (2011) 2091–2097
6.02–5.94 (m, 1H, CHCH2), 5.31–5.26 (m, 1H, CHCH2), 5.23–5.20
(m, 1H, CHCH2), 4.55 (d, 1H, J1,2 = 9.8 Hz, H-1), 4.46–4.41 (m, 1H,
OCH2CHCH2), 4.23–4.18 (m, 1H, OCH2CHCH2), 3.80–3.77 (m, 1H,
H-5), 3.68–3.62 (m, 2H, H-3, H-4), 3.44 (t, 1H, H-2), 2.67 (d, 1H,
OH), 2.18 (d, 1H, OH), 1.36 (d, 3H, H-6); 13C NMR (CDCl3): d
134.6, 131.5, 130.6, 129.3, 128.8, 134.6 (CHCH2), 118.0 (CHCH2),
87.4 (C-1), 77.9 (C-2), 75.3, 74.5 (C-3, C-4), 74.2 (OCH2CHCH2),
71.7 (C-5), 16.6 (C-6). Anal. Calcd for C15H20O4S: C, 60.79; H,
6.80; S, 10.82. Found: C, 60.71; H, 7.00; S, 10.89.
(dd, 1H, J1a,2 = 3.5 Hz, H-1aE), 3.99 (m, 1H, J1b,2 = 8.1 Hz, H-2E),
3.68 (dd, 1H, H-1bE), 2.35 (d, 1H, J2,OH = 4.2 Hz, OH), 1.82 (m, 1H,
H-4aE), 1.61 (m, 1H, H-4bE), 1.30–1.10 (m, 30H, 15CH2), 0.87 (t,
3H, CH2CH3); 13C NMR (CDCl3): d 138.2, 133.4, 129.1, 128.4,
126.1, 123.6, 100.4 (C-1), 83.6 (C-2E), 73.2 (C-3E), 72.3 (C-3), 69.2
(C-2), 69.1 (C-5), 68.0 (C-1E), 66.9 (C-4), 65.0 (C-6). Anal. Calcd
for C54H67N3O11: C, 69.43; H, 7.23; N, 4.50. Found: C, 69.55; H,
7.06; N, 4.35.
3.10. O-(4,6-Di-O-benzyl-2-deoxy-3-O-p-methoxybenzyl-2-
3.8. Phenyl 4-O-acetyl-2-O-allyl-3-O-p-methoxybenzyl-1-thio-b-
trichloroacetamide-b-
D-glucopyranosyl)-(1?2)-O-(3,4,6-tri-O-
L
-fucopyranoside (11)
benzoyl- -mannopyranosyl)-(1?1)-(2S,3R)-2-azido-3-O-
a-D
benzoyl-1,3-eicosanediol (14)
A suspension of 10 (9.94 g, 33.5 mmol) and dibutyltin oxide
(13.3 g, 53.6 mmol) in benzene (500 mL) was heated under reflux
for 16 h with azeotropic removal of water. The mixture was con-
centrated till 250 mL and NaH (5.36 g, 134 mmol), p-methoxyben-
zyl chloride (11.8 mL, 87.0 mmol) and tetrabutylammonium iodide
(32.2 g, 87.2 mmol) were added. The mixture was then heated un-
der reflux for 5 h. The reaction was quenched by the addition of
MeOH and co-evaporated twice with toluene. The residue was dis-
solved in CH2Cl2 and washed with saturated aqueous NaHCO3 and
brine. The organic phase was dried and concentrated in vacuo. The
residue was roughly purified using flash chromatography (1:2
EtOAc–hexane) to afford 3-O-protected derivative (12.7 g). After
drying over P2O5, the derivative was dissolved in Ac2O (25.0 mL)
and pyridine (22.0 mL). After 7 h, MeOH was added to the reaction
mixture on ice and diluted with CH2Cl2 (66 mL). After MeOH evap-
oration, the organic phase was washed with 2 M HCl, saturated
aqueous NaHCO3, and brine, dried, and concentrated. The residue
was purified using flash chromatography (1:4 EtOAc–hexane) to
To a solution of 13 (565 mg, 0.569 mmol) and 6 (600 mg,
0.853 mmol) in CH2Cl2 (4.9 mL) were added NIS (345 mg,
1.53 mmol) and molecular sieves 4 Å (565 mg), and the stirring
was continued at rt for 20 min. To the mixture was added TfOH
(5.00
l
L, 57.0
l
mol) at ꢀ15 °C, and stirred at ꢀ15 °C for 1 h. The
processing of the reaction was performed, as described 13, which
was purified using flash chromatography (1:5 acetone/hexane) to
afford 14 (781 mg, 87%). [
a]
D ꢀ5.9 (c 1.1, CHCl3); 1H NMR (CDCl3):
d 8.01–7.10 (m, 34H, 6Ph, p-MeOC6H4), 6.93 (d, 1H, JNH,2 = 7.2 Hz,
NH2), 5.85 (t, 1H, J3,4 = 9.8 Hz, J4,5 = 9.6 Hz, H-41), 5.52 (dd, 1H, H-
31), 5.20 (m, 1H, H-3E), 5.03 (d, 1H, J1,2 = 7.9 Hz, H-12), 4.87 (d,
1H, J1,2 = 1.5 Hz, H-11), 4.66–4.60 (m, 2H, 2CHHPh), 4.53–4.49 (m,
2H, J5,6a = 3.8 Hz, CHHPh, H-6a1), 4.45 (d, 1H, H-21), 4.42 (d, 1H,
CHHPh), 4.33 (dd, 1H, J5,6b = 5.0 Hz, H-6b1), 4.22 (m, 1H, H-51),
4.11 (t, 1H, H-32), 4.00–3.90 (m, 2H, CHHPh, H-2E), 3.89–3.82 (m,
2H, CHHPh, H-1aE), 3.70 (s, 3H, CH2PhCH3), 3.67 (d, 1H, H-1bE),
3.61–3.54 (m, 2H, H-42, H-6a2), 3.42–3.36 (m, 2H, H-22, H-52),
3.27 (d, 1H, H-62), 1.75 (m, 1H, H-4aE), 1.53 (m, 1H, H-4bE), 1.30–
1.00 (m, 30H, 15CHE), 0.79 (t, 3H, CH2CHE); 13C NMR (CDCl3): d
afford 11 (9.41 g, 61% yield of two steps). [
a
]D ꢀ21.9 (c 1.0, CHCl3);
1H NMR(CDCl3): d 7.56 (m, 2H, SPh), 7.30–7.22 (m, 5H, SPh, p-
MeOC6H4), 6.64 (m, 2H, p-MeOC6H4) 6.00–5.93 (m, 1H, CHCH2),
5.33 (dd, 1H, J3,4 = 3.4 Hz, J4,5 = 0.8 Hz, H-4), 5.27–5.17 (m, 2H,
CHCH2), 4.64 (d, 1H, J = 10.9 Hz, OC6H4CHH), 4.57 (d, 1H,
J1,2 = 9.4 Hz, H-1), 4.43 (d, 1H, J = 10.9 Hz, OC6H4CHH), 4.23 (m,
2H, OCH2CHCH2) 3.78 (s, 3H, OCH3), 3.66 (dq, 1H, J4,5 = 0.8 Hz,
J5,6 = 6.4 Hz, H-5), 3.55 (dd, 1H, J2,3 = 9.4 Hz, J3,4 = 3.4 Hz, H-3),
3.49 (t, 1H, J1,2 = J2,3 = 9.4 Hz, H-2), 2.14 (s, 3H, COCH3), 1.23 (d,
3H, J5,6 = 6.4 Hz, H-6); 13C NMR (CDCl3): d 170.8 (OCOCH3), 159.2,
133.8, 131.8, 129.8, 129.7, 129.6, 129.2, 128.7, 127.3, 116.9,
113.7, 113.5, 134.9 (CHCH2), 116.8 (CHCH2), 87.4 (C-1), 80.6 (C-
3), 76.2 (C-2), 74.4 (OCH2CHCH2), 72.9 (C-5), 71.5 (OC6H4CH2),
69.7 (C-4), 55.2 (CH3OC6H4), 20.9 (OCOCH3) 16.7 (C-6). Anal. Calcd
for C25H30O6S: C, 65.48; H, 6.59; S, 6.99. Found: C, 65.53; H, 6.45; S,
6.77.
2
3
166.0, 165.6, 165.3, 159.3, 138.0, 137.9, 133.4, 133.3, 133.1,
132.9, 130.0, 129.9, 129.8, 129.8, 129.7, 129.6, 129.5, 129.4,
128.5, 128.4, 128.3, 128.2, 128.1, 127.7, 127.6, 127.5, 127.3,
113.8, 98.3 (C-11), 98.2 (C-12), 92.2, 79.1 (C-32), 78.4 (C-42), 75.1
(CH2Ph), 74.9 (C-21), 74.8 (C-22), 74.6 (CH2Ph), 73.4 (CH2Ph), 73.0
(C-3E), 70.7 (C-31), 69.3 (C-51), 68.6 (C-62), 67.4 (C-1E), 67.1 (C-
41), 63.3 (C-2E), 63.3 (C-61), 59.0 (C-52), 55.2, 31.9, 31.5, 29.7,
29.6, 29.6, 29.6, 29.5, 29.4, 29.4, 29.3, 25.3, 22.7, 22.6, 14.1 (CHE3).
Anal. Calcd for C84H97Cl3N4O17: C, 65.47; H, 6.34; N, 3.64. Found:
C, 65.62; H, 6.26; N, 3.43.
3.11. O-(4,6-Di-O-benzyl-2-deoxy-2-trichloroacetamide-b-
glucopyranosyl)-(1?2)-O-(3,4,6-tri-O-benzoyl-
D-
a-D-
mannopyranosyl)-(1?1)-(2S,3R)-2-azido-3-O-benzoyl-1,3-
eicosanediol (15)
3.9. O-(3,4,6-Tri-O-benzoyl-a-D-mannopyranosyl)-(1?1)-
(2S,3R)-2-azido-3-O-benzoyl-1,3-eicosanediol (13)
To a solution of 14 (826 mg, 0.521 mmol) in 10:1 CH3CN–H2O
(8.0 mL) was added CAN (795 mg, 1.45 mmol) at 0 °C. The mixture
was stirred at rt for 90 min. The mixture was diluted with CH2Cl2
and washed with saturated aqueous NaHCO3 and brine. The organ-
ic phase was dried, filtered, and concentrated. The residue was
purified using flash chromatography (1:4 acetone/hexane) to af-
To a solution of 3 (319 mg, 0.694 mmol) and 1212 (406 mg,
0.694 mmol) in CH2Cl2 (7.6 mL) were added NIS (436 mg,
1.87 mmol) and molecular sieves 4 Å (319 mg) and the stirring
was continued at rt for 20 min. To the mixture was added AgOTf
(35.0 mg, 139
l
mol) at 0 °C, and stirred at 0 °C for 1 h. The mixture
ford 15 (573 mg, 77%). [
a]
ꢀ4.5 (c 1.0, CHCl3); 1H NMR (CDCl3):
D
was diluted with CH2Cl2 and neutralized by Et3N. Precipitates were
filtered off and washed with saturated aqueous NaHCO3, 1 M aque-
ous Na2S2O3, and brine. The organic phase was dried, filtered, and
concentrated. The residue was purified using flash chromatogra-
d 8.06–7.10 (m, 30H, 6Ph), 7.03 (d, 1H, JNH,2 = 7.2 Hz, NH2), 5.90
(t, 1H, J3,4 = J4,5 = 10.0 Hz, H-41), 5.59 (dd, 1H, J2,3 = 3.0 Hz, H-31),
5.29 (m, 1H, H-3E), 4.97 (d, 1H, J1,2 = 1.5 Hz, H-11), 4.92 (d, 1H,
J1,2 = 7.9 Hz, H-12), 4.65 (d, 1H, CHHPh), 4.57–4.52 (m, 3H, CHHPh,
H-21, H-6a1), 4.43 (dd, 1H, H-6b1), 4.30 (m, 1H, H-51), 4.13 (t, 1H,
H-32), 4.07 (d, 1H, CHHPh), 3.98 (m, 1H, J2,3 = 7.6 Hz, H-2E), 3.94
(dd, 1H, H-1aE), 3.92 (d, 1H, CHHPh), 3.66 (dd, 1H, H-1bE), 3.56–
3.42 (m, 4H, H-22, H-42, H-52, H-6a2), 3.35 (dd, 1H, H-6a2), 2.83
(m, 1H, OH-32), 1.82 (m, 1H, H-4aE), 1.62 (m, 1H, H-4bE), 1.34–
1.16 (m, 30H, 15CHE), 0.87 (t, 3H, CH2CHE); 13C NMR (CDCl3): d
phy (1:4 EtOAc–hexane) to afford 13 (489 mg, 75%). [a] +2.8 (c
D
1.0, CHCl3); 1H NMR (CDCl3): d 8.10–7.20 (m, 20H, 4Ph), 5.94 (t,
1H, J3,4 = J4,5 = 10.0 Hz, H-4), 5.69 (dd, 1H, J2,3 = 3.2 Hz, H-3), 5.29
(m, 1H, J2,3 = 4.2 Hz, J3,4a = 4.3 Hz J3,4b = 8.5 Hz, H-3E), 5.03 (d, 1H,
J1,2 = 1.5 Hz, H-1), 4.57 (dd, 1H, J5,6a = 3.0 Hz, H-6a), 4.51 (dd, 1H,
J5,6b = 5.7 Hz, H-6b), 4.40 (m, 1H, H-2), 4.37 (m, 1H, H-5), 4.07
2
3

S. Ueno, S. Horito / Carbohydrate Research 346 (2011) 2091–2097
2095
166.0, 165.9, 165.8, 165.3, 162.3, 137.9, 137.9, 133.4, 133.2, 133.0,
132.9, 129.8, 129.7, 129.7, 129.6, 129.5, 129.4, 129.3, 129.0, 128.5,
128.4, 128.3, 128.2, 128.1, 127.9, 127.8, 127.6, 127.4, 98.8 (C-12),
98.2 (C-11), 92.2, 78.1 (C-42), 75.1 (CH2Ph), 74.9 (C-21), 74.4 (C-
22), 73.3 (CH2Ph), 73.1 (C-3E), 72.6 (C-32), 70.7 (C-31), 69.2 (C-51),
68.6 (C-62), 67.2 (C-1E), 67.1 (C-41), 63.4 (C-2E), 63.1 (C-61), 59.0
(C-52), 31.8, 29.9 (C-4E), 29.6, 29.5, 29.4, 29.3, 29.2, 25.3, 22.6,
CHHPh), 4.46 (dd, 1H, H-6b1), 4.35–4.29 (m, 2H, H-51, CHHPh),
4.18 (t, 1H, H-32), 4.12–4.06 (m, 2H, H-53, CHHPh), 4.01 (m, 1H,
H-2E), 3.96–3.92 (m, 2H, H-1aE, CHHPh), 3.90 (dd, 1H, H-33), 3.80
(s, 3H, CH2PhOCH3), 3.75 (dd, 1H, H-1bE), 3.71–3.66 (m, 3H, H-23,
H-32, H-6a2), 3.53–3.49 (m, 2H, H-22, H-52), 3.42 (dd, H-6b2),
2.12 (s, 3H, COCH3), 1.84–1.77 (m, 2H, H-4aE, OH-23), 1.59 (m,
1H, H-4bE), 1.30–1.17 (m, 30H, 15CH2E), 0.87 (t, 3H, CH2CHE3), 0.84
(d, 3H, H-63); 13C NMR (CDCl3): d 166.0, 137.8, 133.4, 133.3,
129.9, 129.8, 129.6, 128.5, 128.3, 128.2, 127.6, 127.3, 126.8,
126.7, 117.4, 113.9, 99.2 (C-13), 98.1 (C-12), 97.2 (C-11), 92.4,
91.5, 91.2, 78.6, 78.5 (C-42), 76.7 (C-22), 76.2, 75.7, 74.8 (C-21),
74.3 (C-52), 73.4 (C-3E), 73.2, 72.3, 72.2, 71.6, 71.1 (C-31), 68.7,
68.2 (C-1E), 67.3 (C-41), 65.7, 63.7 (C-61), 63.3, 55.2, 53.2, 31.9,
29.9, 29.7, 29.6, 29.6, 29.5, 29.4, 29.3, 22.7, 16.0, 14.1 (CHE3). Anal.
Calcd for C92H109Cl3N4O22: C, 63.90; H, 6.35; N, 3.24. Found: C,
63.74; H, 6.14; N, 3.54.
14.0 (CHE). Anal. Calcd for C76H89Cl3N4O16: C, 64.24; H, 6.31; N,
3
3.94. Found: C, 64.20; H, 6.40; N, 3.82.
3.12. O-(4-O-Acetyl-2-O-allyl-6-deoxy-3-O-p-methoxybenzyl-
-fucopyranosyl)-(1?3)-O-(4,6-di-O-benzyl-2-deoxy-2-
trichloroacetamide-b- -glucopyranosyl)-(1?2)-O-(3,4,6-tri-O-
benzoyl- -mannopyranosyl)-(1?1)-(2S,3R)-2-azido-3-O-
benzoyl-1,3-eicosanediol (16)
a-
L
D
a
-D
To a solution of 15 (573 mg, 0.403 mmol) and 11 (222 mg,
0.484 mmol) in CH2Cl2 (3.5 mL) were added NIS (245 mg,
1.09 mmol) and molecular sieves 4 Å (222 mg) and the stirring
was continued at rt for 15 min. To the mixture was added TfOH
3.14. O-(4-O-Acetyl-2-O-benzoyl-3-O-p-methoxybenzyl-
fucopyranosyl)-(1?3)-O-(4,6-di-O-benzyl-2-deoxy-2-
a-L-
trichloroacetamide-b-
D-glucopyranosyl-(1?2)-O-(3,4,6-tri-O-
(3.60
l
L, 41.0
lmol) at 0 °C, and stirred for 1 h. The processing of
benzoyl- -mannopyranosyl)-(1?1)-(2S,3R)-2-azido-3-O-
a-D
the reaction was performed, as described 13, which was purified
benzoyl-1,3-eicosanediol (18)
using flash chromatography (1:3.5 acetone–hexane) to afford 16
(525 mg, 67%). [
a
]
ꢀ37.5 (c 1.0, CHCl3); 1H NMR (CDCl3): d
To a solution of 17 (375 mg, 217
added pyridine (175 lL, 2.17 mmol) and BzCl (500 ll, 2.17 mmol)
at 0 °C. The mixture was stirred at rt for 5 h. The mixture was di-
luted with CH2Cl2 and washed with 2 M aqueous HCl, saturated
aqueous NaHCO3, and brine. The organic phase was dried, filtered,
and concentrated. The residue was purified using flash chromatog-
l
mol) in CH2Cl2 (0.92 mL) was
D
8.06–6.85 (m, 34H, 6Ph, p-MeOC6H4), 7.11–7.06 (m, 1H, NH2),
5.91(m, 1H, CH2CHCH2), 5.84 (t, 1H, J3,4 = 9.8 Hz, J4,5 = 9.4 Hz, H-
41), 5.59 (dd, 1H, J2,3 = 3.4 Hz, H-31), 5.30–5.16 (m, 5H,
J1,2 = 1.9 Hz, H-13, H-43, H-3E, CHCH2), 5.15 (d, 1H, J3,4 = 3.4 Hz,
J4,5 = 10.2 Hz, H-43), 4.98 (d, 1H, J1,2 = 1.5 Hz, H-11), 4.92 (d, 1H,
J1,2 = 8.3 Hz, H-12), 4.62–4.48 (m, 5H, H-21, H-6a1, 3CHHPh), 4.39
(d, 1H, CHHPh), 4.35–4.29 (m, 2H, H-51, H-6b1), 4.17 (t, 1H, H-
32), 4.14–4.04 (m, 3H, H-53, CH2CHCH2), 4.02–3.93 (m, 3H, H-1aE,
H-2E, CHHPh), 3.86 (dd, 1H, H-33), 3.79 (d, 1H, CHHPh), 3.78 (s,
3H, CH2PhCH3), 3.77–3.62 (m, 4H, H-1bE, H-23, H-42, H-6a2),
3.51–3.44 (m, 2H, H-22, H-52), 3.39 (d, 1H, H-6b2), 2.10 (s, 3H,
COCH3), 1.80 (m, 1H, H-4E), 1.59 (m, 1H, H-4E), 1.30–1.16 (m,
30H, 15CHE2), 0.87 (t, 3H, CH2CH3E), 0.79 (d, 3H, H-63); 13C NMR
(CDCl3): d 166.0, 138.0, 134.9, 132.9, 131.9, 130.1, 129.9, 129.8,
129.7, 129.7, 129.7, 129.6, 129.5, 129.5, 128.5, 128.3, 128.2,
128.1, 127.7, 127.5, 127.4, 127.3, 117.3, 115.5, 113.7, 114.6, 99.0
(C-12), 98.5 (C-11), 98.1 (C-13), 92.4, 92.1, 77.6 (C-42), 76.2 (C-32),
76.2 (C-33), 75.9, 75.4 (C-23), 75.2 (C-22), 74.9, 74.5 (C-52), 74.2
(C-21), 73.7 (C-3E), 73.4 (CH2Ph), 73.2, 71.1, 70.7 (C-31), 70.5 (C-
43), 69.3 (C-51), 68.6 (C-62), 67.5 (C-1E), 67.3 (C-41), 65.2 (C-53),
63.4 (C-2E), 63.3 (C-61), 55.2, 32.0, 30.0 (C-4E), 29.7, 29.6, 29.6,
29.6, 29.5, 29.4, 29.3, 25.3, 22.6, 20.9, 15.9, 14.1 (CHE3). Anal. Calcd
for C95H113Cl3N4O22: C, 64.49; H, 6.44; N, 3.17. Found: C, 64.61; H,
6.48; N, 3.43.
raphy (1:3.5 EtOAc–hexane) to afford 18 (368 mg, 92%). [
a
]D ꢀ58.1
(c 1.0, CHCl3); 1H NMR (CDCl3): d 8.13–6.68 (m, 39H, 7Ph, p-
MeOC6H4), 6.87 (d, 1H, NH2), 5.74 (t, 1H, J3,4 = 9.8 Hz, J4,5 = 9.7 Hz,
H-41), 5.51 (dd, 1H, J2,3 = 3.3 Hz, H-31), 5.42 (d, 1H, J1,2 = 3.8 Hz,
H-13), 5.38 (dd, 1H, J2,3 = 10.3 Hz, H-23), 5.27 (m, 1H, J2,3 = 4.0 Hz,
H-3E), 5.06 (d, 1H, J3,4 = 3.1 Hz, H-43), 4.96–4.92 (m, 2H, H-11, H-
12), 4.59 (d, 1H, CHHPh), 4.55 (d, 1H, CHHPh), 4.48 (dd ,1H ,H-
21), 4.41–4.36 (m, 4H, 2CHHPh, H-6a1, 6b1), 4.31 (t, 1H, H-32),
4.26 (m, 1H, H-51), 4.15 (dd, 1H, J5,6 = 6.6 Hz, H-53), 4.02 (d, 1H,
CHHPh), 3.98 (m, 1H, H-2E), 3.94 (dd, 1H, H-33), 3.87 (d,1H,
CHHPh), 3.84 (dd, 1H, H-1aE), 3.71 (s, 3H, CH2PhCH3), 3.70–3.62
(m, 3H, H-1bE, H-22, H-42), 3.52–3.45 (m, 2H, H-52, H-6a2), 3.34
(dd, 1H, H-6b2), 2.15 (s, 3H, COCH3), 1.81 (m, 1H, H-4E), 1.59 (m,
1H, H-4E), 1.30–1.16 (m, 30H, 15CH2), 0.87 (t, 3H, CH2CHE3), 0.71
(d, 3H, H-63); 13C NMR (CDCl3): d 166.0, 165.1, 160.3, 137.6,
133.5, 133.0, 130.1, 129.8, 129.6, 129.5, 129.4, 129.1, 128.6,
128.5, 128.4, 128.3, 128.1, 127.7, 127.6, 127.5, 126.9, 113.7,
113.6, 98.1 (C-12), 97.7 (C-11), 96.7, 96.6 (C-13), 94.0, 93.2, 92.7,
92.1, 89.9, 89.2, 87.0, 86.9, 77.0, 76.9 (C-42) 76.0, 75.5, 75.2 (C-
21), 74.2 (CH2Ph), 73.2 (CH2Ph), 72.3, 72.0, 71.3 (CH2Ph), 70.6 (C-
31), 70.2 (C-43), 69.4, 68.1, 67.9, 67.8, 66.6 (C-41), 66.1, 65.2 (C-
51), 64.8, 63.8, 63.4 (C-61), 61.9, 55.8, 55.1, 55.1, 55.1, 52.7, 31.9,
29.7, 29.6, 29.5, 29.4, 29.3, 22.6, 14.1 (CHE3). Anal. Calcd for
3.13. O-(4-O-Acetyl-3-O-p-methoxybenzyl-
(1?3)-O-(4,6-di-O-benzyl-2-deoxy-2-trichloroacetamide-b-
glucopyranosyl)-(1?2)-O-(3,4,6-tri-O-benzyl-
a-L-fucopyranosyl)-
D-
a-D-
mannopyranosyl)-(1?1)-(2S,3R)-2-azido-3-O-benzoyl-1,3-
C99H113Cl3N4O23: C, 64.86; H, 6.21; N, 3.06. Found: C, 65.16; H,
eicosanediol (17)
6.34; N, 3.00.
To a solution of 16 (525 mg, 299
(7.86 mL) was added PdCl2 (10.6 mg, 59.8
l
mol) in 2:1 CH3OH–CH2Cl2
mol). The mixture
3.15. O-(4-O-Acetyl-2-O-benzoyl-3-O-p-methoxybenzyl-
fucopyranosyl)-(1?3)-O-(4,6-di-O-benzyl-2-deoxy-2-
a-L-
l
was stirred at rt for 21 h. The mixture was then diluted with
CH2Cl2, filtered, and concentrated. The residue was purified using
flash chromatography (1:4 EtOAc–hexane) to afford 17 (375 mg,
trichloroacetamide-b-
benzoyl- -mannopyranosyl)-(1?1)-(2S,3R)-3-O-benzoyl-2-
octadecanamide-1,3-eicosanediol (21)
D-glucopyranosyl)-(1?2)-O-(3,4,6-tri-O-
a-D
73%). [
a]
ꢀ54.8 (c 1.1, CHCl3); 1H NMR (CDCl3): d 8.06–6.85 (m,
D
34H, 6Ph, p-MeOC6H4), 7.09 (d, 1H, NH2), 5.89 (t, 1H,
J3,4 = J4,5 = 9.8 Hz, H-41), 5.57 (dd, 1H, J2,3 = 3.0 Hz, H-31), 5.30–
5.25 (m, 2H, H-13, H-3E), 5.22 (d, 1H, J3,4 = 3.8 Hz, H-43), 5.15 (d,
1H, J1,2 = 7.9 Hz, H-12), 5.00 (s, 1H, J1,2 = 1.5 Hz, H-11), 4.70 (d, 1H,
CHHPh), 4.62 (d, 1H, CHHPh), 4.54–4.51 (m, 3H, H-21, H-6a1,
To a solution of 18 (294 mg, 160 lmol) in 1:0.04 CH2Cl2–HOAc
(7.8 mL) was added zinc powder (1.67 g, 30.2 mmol) at 0 °C. The
mixture was stirred at 0 °C for 15 min. The mixture was diluted
with CH2Cl2, filtered, and co-evaporated with toluene to yield 19
(212 mg). To a solution of 19 (212 mg, 117 lmol) in CH2Cl2

2096
S. Ueno, S. Horito / Carbohydrate Research 346 (2011) 2091–2097
(7.6 mL) was added stearic acid (60.0 mg, 211
lmol) and WSC
C117H152N2O24: C, 71.32; H, 7.78; N, 1.42. Found: C, 71.47; H,
(44.9 mg, 234 mol). The mixture was stirred at rt for 15 min.
l
7.69; N, 1.20.
The mixture was diluted with CH2Cl2 and washed with saturated
aqueous NaHCO3 and brine. The organic phase was dried, filtered,
and concentrated. The residue was purified using flash chromatog-
raphy (1:1.5 EtOAc–hexane) to afford 21 (169 mg, 55% yield of two
3.17. O-(4-O-Acetyl-2-O-benzoyl-
(4,6-di-O-benzyl-2-acetamido-2-deoxy-b-
a
-
L
-fucopyranosyl)-(1?3)-O-
-glucopyranosyl)-
-mannopyranosyl)-(1?1)-
(2S,3R)-3-O-benzoyl-2-octadecanamido-1,3-eicosanediol (23)
D
(1?2)-O-(3,4,6-tri-O-benzoyl-
a-D
steps). [
a]
ꢀ54.9 (c 0.9, CHCl3); 1H NMR (CDCl3): d 8.10–6.72 (m,
D
39H, 7Ph, p-MeOC6H4), 6.33 (d, 1H, NH2), 6.12 (d, 1H, NHE), 5.62 (t,
1H, J3,4 = 9.6 Hz, H-41), 5.44 (dd, 1H, J2,3 = 3.4 Hz, H-31), 5.42 (d, 1H,
J1,2 = 2.6 Hz, H-13), 5.30–5.25 (m, 2H, H-23, H-3E), 5.04 (d, 1H, H-
43), 4.74–4.68 (m, 2H, H-11, H-12), 4.64–4.58 (m, 2H, 2CHHPh),
4.48 (m, 1H, H-2E), 4.46–4.34 (m, 4H, 2CHHPh, H-21, H-6a1), 4.24
(m, 1H, H-51), 4.19–4.12 (m, 2H, H-32, H-53), 3.96 (dd, 1H, H-33),
3.92 (d, 1H, CHHPh), 3.84–3.76 (m, 2H, H-22, H-1aE) 3.72 (s, 3H,
CH2PhCH3), 3.62 (t, 1H, H-42), 3.61–3.55 (m, 2H, H-52, H-1bE),
3.46 (d, 1H, H-6a2), 3.38 (d, 1H, H-6b2), 2.25 (m, 2H, COCHA2 ),
2.15 (s, 3H, COCH3), 1.73 (m, 2H, H-4aE, H-4bE), 1.66 (m, 2H,
COCH2CHA), 1.36–1.18 (m, 58H, 29CHE;A), 0.88 (t, 6H, CH2CHE;A),
To a solution of 22 (144 mg, 73.2
(1.44 mL) was added CAN (80.3 mg, 146
was stirred at rt for 75 min. The processing of the reaction was per-
formed, as described 15, which was purified using flash chroma-
lmol) in 10:1 CH3CN–H2O
lmol) at 0 °C. The mixture
tography (1:2.5 EtOAc–hexane) to afford 23 (105 mg, 77%). [a]
D
ꢀ37.5 (c 0.8, CHCl3); 1H NMR (CDCl3): d 8.15–7.04 (m, 35H, 7Ph),
6.29 (d, 1H, NHE), 5.66 (t, 1H, J3,4 10.2 Hz, H-41), 5.52 (dd, 1H,
J2,3 = 3.4 Hz, H-31), 5.45 (d, 1H, J,12 = 3.4 Hz, H-13), 5.37 (d, 1H,
NH2), 5.25 (m, 1H, H-3E), 5.13 (dd, 1H, H-23), 4.97 (d, 1H,
J3,4 = 3.4 Hz, J4,5 1.1 Hz, H-43), 4.85 (d, 1H, J1,2 = 7.9 Hz, H-12), 4.74
(d, 1H, J1,2 = 1.9 Hz, H-11), 4.66 (d, 1H, CHHPh), 4.54 (d, 1H, CHHPh),
4.51 (m, 1H, H-2E), 4.35 (dd, 1H, H-6a1), 4.33–4.23 (m, 4H, H-21, H-
6b1, H-32, H-33), 4.18 (dd, 1H, H-53), 4.10 (d, 1H, CHHPh), 3.97 (d,
1H, CHHPh), 3.86 (dd, 1H, H-1aE), 3.63 (dd, 1H, H-1bE), 3.61 (t, 1H,
H-42), 3.55 (dd, 1H, H-52), 3.47 (dd, 1H, H-6a2), 3.41 (dd, 1H, H-
6b2), 3.34 (m, 1H, H-22), 2.26 (m, 2H, COCHA2 ), 2.15 (s, 3H,
2
2
3
0.72 (d, 3H, H-63); 13C NMR (CDCl3): d 166.1, 165.1, 157.4, 138.5,
138.2, 137.9, 135.4, 133.2, 133.1, 133.1, 132.3, 131.8, 131.6,
131.0, 130.9, 129.9, 129.7, 129.7, 129.7, 129.5, 128.4, 128.4,
128.3, 128.3, 128.2, 128.1, 127.6, 127.1, 127.0, 113.7, 99.3 (C-12),
99.2 (C-11), 97.8, 97.1, 96.0 (C-13), 89.9, 86.7, 83.7, 79.9, 77.3 (C-
42), 75.7, 75.4 (C-21), 74.9, 74.8, 74.5, 73.3, 73.2, 73.0, 72.9, 72.9,
72.5, 72.1, 71.8, 71.7 (C-2E), 71.5 (2 ꢁ CH2Ph), 71.3, 71.2 (C-31),
71.1 (C-43), 69.0, 68.9, 67.4 (C-33, C-41), 64.7, 63.5 (C-61), 61.4,
60.5, 60.4, 59.9, 55.2, 55.1, 52.6, 31.9, 29.7, 29.6, 29.5, 29.4, 25.8,
22.7, 21.0, 20.9, 15.6, 14.1. Anal. Calcd for C117H149Cl3N2O24: C,
67.76; H, 7.24; N, 1.35. Found: C, 67.56; H, 7.04; N, 1.47.
COCH3Þ, 2.04 (s, 3H, COCH23), 1.80 (m, 1H, H-4aE), 1.75 (m, 1H, H-
3
4bE), 1.65 (m, 2H, COCH2CHA), 1.36–1.18 (m, 58H, 29CHE;A), 0.88
2
2
(t, 6H, CH2CHE;A), 0.70 (d, 3H, H-63); 13C NMR (CDCl3): d 165.5,
3
133.7, 133.0, 133.0, 129.8, 129.7, 129.6, 129.5, 129.3, 128.3,
128.1, 127.5, 127.4, 127.0, 102.8, 99.3 (C-12), 98.7 (C-11), 97.8,
96.1 (C-13), 91.9, 77.1 (C-42), 74.8 (C-52, C-43), 74.6 (C-3E), 74.5
(C-21), 74.2 (CH2Ph), 73.6 (CH2Ph), 72.0 (C-23), 70.8 (C-31), 69.9,
69.0 (C-62), 68.5, 68.0 (C-51), 67.6, 67.4 (C-41), 67.2, 66.8 (C-1E),
65.9, 64.9 (C-53), 64.0, 63.6, 53.4, 36.8, 31.9, 29.7, 29.6, 29.4, 29.3,
25.8, 23.0, 22.7, 14.1. Anal. Calcd for C109H144N2O23: C, 70.75; H,
7.84; N, 1.51. Found: C, 70.91; H, 8.11; N, 1.36.
3.16. O-(4-O-Acetyl-2-O-benzoyl-3-O-p-methoxybenzyl-
fucopyranosyl)-(1?3)-O-(4,6-di-O-benzyl-2-acetamido-2-
deoxy-b- -glucopyranosyl)-(1?2)-O-(3,4,6-tri-O-benzoyl-
a
-
L
-
-
D
a
D
-
mannopyranosyl)-(1?1)-(2S,3R)-3-O-benzoyl-2-
octadecanamido-1,3-eicosanediol (22)
To a solution of 21 (169 mg, 81.4
l
mol) in benzene (2.87 mL)
3.18. O-(Triethylammonium 4-O-acetyl-2-O-benzoyl-3-O-
was added Bu3SnH (0.973 mL, 3.67 mmol), N,N-dimethylacetamide
sulfonato-
acetamido-2-deoxy-b-
benzoylzoyl- -mannopyranosyl)-(1?1)-(2S,3R)-3-O-benzoyl-
2-octadecanamido-1,3-eicosanediol (24)
a
-
L
-fucopyranosyl)-(1?3)-O-(4,6-di-O-benzyl-2-
(0.470 mL) and 2,20-azobisisobutyronitrile (AIBN; 3.16 mg,
D-glucopyranosyl)-(1?2)-O-(3,4,6-tri-O-
19.5
centrated. The residue was purified using flash chromatography
(1:1.5 EtOAc–hexane) and gave 22 (144 mg, 98%). [
ꢀ63.9 (c
lmol). The mixture was stirred at 120 °C for 30 min and con-
a-D
a]
D
0.9, CHCl3); 1H NMR (CDCl3): d 8.10–6.77 (m, 39H, 7Ph, p-
MeOC6H4), 6.40 (d, 1H, NHE), 5.62 (t, 1H, J3,4 = 9.8 Hz,H-41), 5.50
(dd, 1H, J2,3 3.4 Hz, H-31), 5.48 (d, 1H, J1,2 = 4.2 Hz, H-13), 5.39 (d,
1H, NH2), 5.25 (m, 1H, H-3E), 5.18 (dd, 1H, J2,3 = 10.6 Hz, H-23),
5.06 (d, 1H, J3,4 = 3.4 Hz, H-43), 4.82 (d, 1H, J1,2 = 8.3 Hz, H-12),
4.71 (d, 1H, H-11), 4.64–4.58 (t, 2H, 2CHHPh), 4.50 (m, 1H, H-2E),
4.44 (d, 1H,CHHPh), 4.42 (d, 1H, CHHPh), 4.37–4.28 (m, 4H, H-21,
H-6a1, H-6b1, H-32), 4.24 (m, 1H, H-51), 4.12 (d, 1H, H-53), 4.08
(d, 1H, CHHPh), 3.98 (dd, 1H, H-33), 3.95 (d, 1H, CHHPh), 3.86
(dd, 1H, H-1aE), 3.74 (s, 3H, PhOCH3), 3.63 (dd, 1H, H-1bE), 3.55–
3.50 (m,2H, H-42, H-52), 3.42 (d, 1H, H-6a2), 3.37 (d, 1H, H-6b2),
3.24 (m, 1H, H-22), 2.26 (m, 2H, COCH2A), 2.13 (s, 3H, COCH33),
2.05 (s, 3H, COCH22), 1.77 (m, 2H, H-4aE, H-4bE), 1.65 (m, 2H,
COCH2CHA), 1.36–1.18 (m, 58H, 29CHE;A), 0.88 (t, 6H, CH2CHE;A),
To a solution of 23 (105 mg, 56.6
lmol) in DMF (7.60 mL) was
added pyridine sulfur trioxide complex (55.2 mg, 347
lmol). The
mixture was stirred at rt for 60 min. The mixture was diluted with
CH2Cl2, neutralized by Et3N, and co-evaporated several times with
toluene. The residue was purified using flash chromatography
(40:1 EtOAc–MeOH) to afford 24 (89.9 mg, 79%). [
a
]
ꢀ37.5 (c
D
0.8, CHCl3); 1H NMR (CDCl3): d 8.10–6.96 (m, 35H, 7Ph), 5.68 (d,
1H H-33), 5.66 (t, 1H, J3,4 = 10.2 Hz, H-41), 5.58 (dd, 1H,
J2,3 = 3.4 Hz, H-31), 5.36 (s, 1H, H-13), 5.30 (m, 1H, H-3E), 5.16–
5.08 (m, 2H, H-23, H-43), 4.75 (s, 1H, H-11), 4.70 (d, 1H, H-12),
4.64 (d, 1H, CHHPh), 4.60–4.51 (m, 2H, H-2E, CHHPh), 4.50–4.13
(m, 6H, H-21, H-51, H-6a1, H-6b1, H-32, H-53), 4.10 (d, 1H, CHHPh),
3.98–3.90 (m, 2H, H-1aE, CHHPh), 3.64–3.50 (m, 3H, H-1bE, H-42,
H-52), 3.48–3.36 (m, 2H, H-6a2, H-6b2), 3.27 (m, 1H, H-22), 2.90–
2
2
3
0.70 (d, 3H, H-63); 13C NMR (CDCl3): d 165.7, 164.1, 157.1, 157.0,
153.9, 153.8, 137.9, 136.0, 131.6, 129.7, 129.7, 129.5, 129.4,
128.6, 128.5, 128.3, 128.2, 128.1, 127.5, 110.7, 105.3, 101.9 (C-
22), 98.7 (C-11), 97.7, 97.0, 95.2 (C-13), 93.9, 91.6 (C-12), 91.5,
91.4, 91.3, 90.5, 87.5 (C-2E), 85.1, 84.5, 84.1, 76.8 (C-42), 75.8,
75.0 (C-52), 74.7 (C-3E), 74.7 (C-21), 73.2 (CH2Ph), 72.2 (CH2Ph),
71.1 (CH2Ph), 70.8 (C-31), 70.7 (C-23), 70.6 (C-43), 70.4, 70.3, 68.8
(C-51, C-62), 68.0, 67.9, 67.4 (C-41), 66.7, 66.5 (C-1E), 66.2, 64.6
(C-53), 64.2, 64.1, 63.5 (C-61), 60.3 (C-32), 57.9, 55.1, 45.0, 38.0,
35.1, 31.9, 29.7, 29.6, 29.4, 29.3, 22.6, 21.5, 14.1. Anal. Calcd for
2.70 (m, 6H, 3NCH2CH3), 2.39 (m, 2H, COCHA), 2.08 (s, 3H,
2
COCH33), 1.89 (s, 3H, COCH23), 1.80 (m, 2H, C-4aE, C-4bE), 1.73–
1.58 (m, 2H, COCH2CHA), 1.44–1.10 (m, 67H, 3NCH2CH3, 29CHE;A),
2
2
0.87 (t, 6H, CH2CHE;A), 0.80 (d, 3H, H-63); 13C NMR (CDCl3): d
3
168.0, 143.7, 135.4, 134.4, 134.3, 134.2, 130.1, 130.0, 129.9,
129.8, 129.7, 128.8, 128.6, 128.5, 128.4, 127.6, 117.3, 117.2,
115.4, 114.5, 111.6, 98.4 (C-12), 98.3 (C-11), 97.1, 96.3, 95.4 (C-
13), 94.7, 92.7, 77.3 (C-42), 74.9 (C-3E), 74.7 (CH2Ph), 74.6 (C-52),
74.5 (C-21), 73.9 (C-43), 73.8, 73.4 (CH2Ph), 73.1, 72.4, 72.1, 71.4
(C-31), 69.6, 68.5 (C-51), 68.1 (C-62), 67.9 (C-41), 67.4, 65.9 (C-1E),

S. Ueno, S. Horito / Carbohydrate Research 346 (2011) 2091–2097
2097
65.5, 64.8 (C-53), 63.6, 60.0, 58.2, 57.7, 57.5, 52.7, 51.3, 36.7, 36.0,
35.9, 32.0, 31.9, 29.7, 29.6, 29.5, 29.4, 26.1, 22.7, 22.7, 14.0. Anal.
Calcd for C115H159N3O26S: C, 67.99; H, 7.89; N, 2.07; S, 1.58. Found:
C, 68.58; H, 7.54; N, 2.59; S, 1.63.
19 h, then neutralized with Amberlite IR-120 (H+) resin until pH
7 and the mixture was filtered. The resin was washed with MeOH,
and combined filtrate and washings were concentrated. The resi-
due was purified using column-chromatography (15:1 EtOAc–
MeOH) on Sephadex LH-20 (2 g) to afford 1 (16.1 mg, 14.5 lmol,
3.19. O-(Triethylammonium 4-O-acetyl-2-O-benzoyl-3-O-
86%). [
a
]
ꢀ32.9 (c 1.0, CHCl3); 1H NMR (CDCl3): d 5.02 (d, 1H,
D
sulfonato-
a
-L
-fucopyranosyl)-(1?3)-O-(2-acetamido-2-deoxy-
J1,2 = 1.9 Hz, H-13), 4.78 (d, 1H, J1,2 = 1.5 Hz, H-11), 4.58 (d, 1H,
J1,2 = 9.4 Hz, H-12), 4.50 (dd, 1H, H-33), 4.37 (dd, 1H, H-41), 4.22
(s, 1H, H-31), 4.08 (d, 1H, H-43), 4.00 (dd, 1H, H-23), 3.95–3.86
(H-21, H-2E), 3.82–3.74 (m, 3H, H-6a1, H-6b1, H-32), 3.68–3.56
(H-51, H-53), 3.52 (t, 1H, H-42), 3.49–3.44 (m, 2H, H-6a2, H-6b2),
3.38 (m, 1H, H-22), 2.22 (m, 2H, COCH2A), 2.03 (s, 3H, COCH3),
1.68–1.56 (m, 2H, H-4aE, H-4bE), 1.55–1.50 (m, 2H, COCH2CHA2 ),
b- -glucopyranosyl)-(1?2)-O-(3,4,6-tri-O-benzoyl-a-D-
D
mannopyranosyl)-(1?1)-(2S,3R)-3-O-benzoyl-2-
octadecanamido-1,3-eicosanediol (25)
Compound 24 (46.6 mg, 23.5
(2.0 mL) and then solution of sodium bromate (33.2 mg,
141 mol) in water (1.4 mL) was added. To the well stirred two-
lmol) was dissolved in EtOAc
a
l
1.49–1.18 (m, 61H, 29CHE2;A, H-63), 0.88 (t, 6H, CH2CHE;A); 13C
3
phase system an aqueous solution of sodium dithionite (80% pure,
38.2 mg, dissolved in 3.0 mL water) was added and stirred for 4 h.
The mixture was diluted with EtOAc and the organic phase was
successively washed with 1 M aqueous Na2S2O3 and brine. The or-
ganic phase was dried, filtered, and concentrated. The residue was
purified using flash chromatography (15:1 EtOAc–MeOH) to afford
NMR (CDCl3): d 168.1, 158.0, 140.9, 111.0, 98.3 (C-11), 92.9 (C-
12), 87.4 (C-13), 80.6, 74.8, 73.3, 72.6, 70.9, 70.8, 70.7, 70.6 (C-43),
68.1 (C-31), 66.8, 66.7, 62.5, 61.8, 61.0, 54.7, 53.7, 53.0, 44.0, 33.5,
31.6, 29.4, 29.4, 29.3, 29.0, 22.3, 13.4. Anal. Calcd for
C58H109N2NaO20S: C, 57.59; H, 9.08; N, 2.32; S, 2.65. Found: C,
57.26; H, 9.59; N, 2.81; S, 2.79.
25 (40.0 mg, 33%). [
a
]
ꢀ25.9 (c 0.9, CHCl3); 1H NMR (CDCl3): d
D
8.05–7.31 (m, 25H, 5Ph), 5.74 (t, 1H, J3,4 = 10.2 Hz, H-41), 5.60 (d,
1H, H-33), 5.52 (d, 1H, J1,2 = 1.9 Hz, H-13), 5.40 (dd, 1H,
J2,3 = 3.4 Hz, H-31), 5.28 (m, 1H, H-3E), 5.23–5.20 (m, 2H, H-23, H-
43), 4.77 (d, 1H, J1,2 = 1.5 Hz, H-11), 4.68 (d, 1H, J1,2 = 8.3 Hz, H-
12), 4.53 ((m, 1H, H-2E), 4.48–4.43 (m, 4H, H-21, H-6a1, H-6b1, H-
53), 4.32 (m, 1H, H-51), 4.01–3.93 (m, 2H, H-32, H-1aE), 3.64–3.52
(m, 3H, H-22, H-52, H-1bE), 3.39 (t, 1H, H-42), 3.35–3.30 (m, 2H,
H-6a2, H-6b2), 3.21 (s, 1H, OH2), 3.08 (s, 1H, OH2), 2.90–2.70 (m,
6H, 3NCH2CH3), 2.39 (m, 2H, COCHA), 2.20 (s, 3H, COCH2), 1.98
Acknowledgment
This work was supported by the City Area Program ‘Chiba/Toka-
tsu Area (Basic Stage)’ of the Ministry of Education, Culture, Sport,
Science and Technology of the Japanese Government.
References
1. Sun, J.; Thurin, J.; Cooper, H. S.; Wang, P.; Mackiewicz, M.; Steplewski, Z.;
Blaszczyk-Thurin, M. Proc. Natl. Acad. Sci. U.S.A. 1995, 92, 5724–5728.
2. Walz, G.; Aruffo, A.; Kolanus, W.; Bevilacqua, M.; Seed, B. Science 1990, 250,
1132–1135.
3. Labarrière, N.; Piau, J. P.; Otry, C.; Denis, M.; Lustenberger, P.; Meflah, K.; Le
Pendu, J. Cancer Res. 1994, 54, 6275–6281.
2
3
(s, 3H, COCH33), 1.86–1.59 (m, 2H, H-4aE, H-4bE), 1.32 (m, 2H,
COCH2CHA), 1.30–1.17 (m, 67H, 3NCH2CH3, 29CHE;A), 1.16 (d, 3H,
2
2
H-63), 0.88 (t, 6H, CH2CHE;A); 13C NMR (CDCl3): d 163.4, 156.7,
3
152.6, 140.2, 139.1, 138.2, 133.7, 130.0, 129.9, 129.8, 129.7,
129.6, 129.3, 128.8, 128.7, 128.6, 128.3, 127.7, 126.9, 123.9,
120.5, 120.4, 120.3, 117.1, 115.2, 113.3, 111.5, 98.6 (C-11), 98.2
(C-12), 95.5 (C-13), 88.6, 88.3, 78.9, 78.7, 78.2, 76.9, 76.4, 75.1,
74.7, 74.4, 74.2, 73.9, 73.7, 69.6, 69.4, 69.0, 64.9, 62.5, 59.9, 57.8,
54.5, 32.0, 31.9, 29.7, 29.6, 29.4, 22.7, 14.0.
4. Martín-Satué, M.; Marrugat, R.; Cancelas, J. A.; Blanco, J. Cancer Res. 1998, 58,
1544–1550.
5. Kannagi, R.; Izawa, M.; Koike, T.; Miyazaki, K.; Kimura, N. Cancer Sci. 2004, 95,
377–384.
6. Chandrasekaran, E. V.; Xue, J.; Neelamegham, S.; Matta, K. L.; Wulf, G.; Röhle, G.
Carbohydr. Res. 2006, 341, 983–994.
7. Wu, D.; Fujio, M.; Wong, C. H. Bioorg. Med. Chem. 2008, 16, 1073–1083.
8. Giabbai, B.; Sidobre, S.; Crispin, M. D. M.; Sanchez-Ruìz, Y.; Bachi, A.;
Kronenberg, M.; Wilson, I. A.; Degano, M. J. Immunol. 2005, 175, 977–984.
9. Maetel, A.; Banville, J.; Aruffo, A. A. Eur. Pat. Appl. 1995, 86.
10. Bélot, F.; Jacquinet, J.-C. Carbohydr. Res. 2000, 325, 93–106.
11. Johnstone, J. N.; Paquette, L. A. Tetrahedron Lett. 1995, 36, 4341–4344.
12. Lichtenthaler, F. W.; Lergenmuller, M.; Peters, S.; Varga, Z. Tetrahedron:
Asymmetry 2003, 14, 727–736.
3.20. O-(Sodium 3-O-sulfonato-a-L-fucopyranosyl)-(1?3)-O-(2-
acetamido-2-deoxy-b- -glucopyranosyl)-(1?2)-O-(a-D-
D
mannopyranosyl)-(1?1)-(2S,3R)-2-octadecanamide-1,3-
eicosanediol (1)
13. Bock, K.; Pedersen, C. J. Chem. Soc., Perkin Trans. 2 1974, 293–297.
14. Adinolfi, M.; Barone, G.; Guariniello, L.; Iadonisi, A. Tetrahedron Lett. 1999, 40,
8439–8441.
To a solution of 25 (30.9 mg 16.9
added 0.5 M NaOMe in MeOH (144
l
mol) in MeOH (3.1 mL) was
lL), and stirred at rt for 2 h,
and water (1.0 mL) was added. The solution was stirred at rt for