Biotinylated Oligo-α-(1 → 4)-d-galactosamines and Their N-Acetylated Derivatives: α-Stereoselective Synthesis and Immunology Application

Article abstract of DOI:10.1021/jacs.9b11703

Using 3-O-benzoyl-4,6-O-di-tert-butylsilylidene-2-azido-2-deoxy-selenogalactoside, biotinylated oligo-α-(1 → 4)-d-galactosamines comprising from two to six GalN units were prepared for the first time together with their N-acetylated derivatives. The combination of blocking groups used herein provided stereocontrol for the α-stereospecific glycosylation, to show also high efficiency of phenyl 2-azido-2-deoxy-selenogalactosides as glycosyl donors. The obtained glycoconjugates are related to fragments of exopolysaccharide galactosaminogalactan (GG) found in Aspergillus fumigatus, which is the most important airborne human fungal pathogen in industrialized countries. The synthesized glycoconjugates were arrayed on streptavidin-coated plates and used to investigate the GG epitopes recognized by mouse monoclonal antibodies against GG and by human antibodies in the sera of patients with aspergillosis. The obtained data showed that the oligo-α-(1 → 4)-d-galactosamines and their N-acetylated derivatives allowed the first precise analysis of the specificity of the antibody responses to this extremely complex fungal polysaccharide.

Full text of DOI:10.1021/jacs.9b11703

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Communication
Biotinylated oligo-#-(1#4)-D-galactosamines and their N-acetylated
derivatives: #-stereoselective synthesis and immunology application
Ekaterina D. Kazakova, Dmitry V. Yashunsky, Vadim B. Krylov, Jean-Philippe Bouchara,
Murielle Cornet, Isabel Valsecchi, Thierry Fontaine, Jean-Paul Latge, and Nikolay E. Nifantiev
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.9b11703 • Publication Date (Web): 08 Jan 2020
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Ekaterina D. Kazakova , Dmitry V. Yashunsky , Vadim B. Krylov , Jean-Philippe Bouchara , Murielle
Cornet , Isabel Valsecchi , Thierry Fontaine , Jean-Paul Latgꢀ , and Nikolay E. Nifantiev*
‡
§,
§,
§,
⊥
,†
∥
∥
†
N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky prospect 47, 119991 Moscow,
Russian Federation
#
Laboratoire de Parasitologie Mycologie, CHU Angers, France
‡
University of Grenoble Alpes, CNRS, CHU Grenoble Alpes, Grenoble INP, TIMC-IMAG, Grenoble, France
§
Unitꢀ des Aspergillus, Institut Pasteur, Paris, France
∥
Fungal Biology and Pathogenicity Unit Institut Pasteur, Paris, France
⊥
School of Medicine, University of Crete Heraklion, Greece
Supporting Information
Herein, we describe the first synthesis of oligo-α-(1→4)-D-
galactosamines (35-39, Scheme 2) comprising from 2 to 6 mono-
saccharide units and containing biotinylated aglycon-spacer as
well as of their N-acetylated derivatives (41-45). Galactosamini-
des 34 and 40 were also synthesized.
ABSTRACT Using 3-O-benzoyl-4,6-O-di-tert-butylsilylidene-2-
azido-2-deoxy-selenogalactoside, biotinylated oligo-α-(1→4)-D-
galactosamines comprising from 2 to 6 GalN units were prepared for
the first time together with their N-acetylated derivatives. The combi-
nation of blocking groups used herein provided stereocontrol for the α-
stereospecific glycosylation, to show also high efficiency of phenyl 2-
azido-2-deoxy-selenogalactosides as glycosyl donors. The obtained
glycoconjugates are related to fragments of exopolysaccharide galac-
tosaminogalactan (GG) found in Aspergillus fumigatus, which is the
most important airborne human fungal pathogen in industrialized
countries. The synthesized glycoconjugates were arrayed on streptavi-
din-coated plates and used to investigate the GG epitopes recognized
by mouse monoclonal antibodies against GG and by human antibodies
in the sera of patients with aspergillosis. The obtained data showed that
the oligo-α-(1→4)-D-galactosamines and their N-acetylated derivatives
allowed the first precise analysis of the specificity of the antibody re-
sponses to this extremely complex fungal polysaccharide.
The assembly of the target oligosaccharides is a complex task
because the α-(1,2-cis)-stereoselectivity of the glycosylation must
be controlled and the axial 4-OH group of the galactopyranose
units have relatively low reactivity. In this context, the use of a 2-
azido-2-deoxygalactosyl donor with a “nonparticipating” N -
group should facilitate both α-stereoselective galactosylation and
3
7
offer a free NH group during GalN-unit generation when re-
2
quired.
Based on the above considerations, the target oligosaccharides
were synthesized using selectively O-substituted phenyl 2-azido-
-deoxy-selenogalactoside 5 (Scheme 1), which belongs to a new
2
8
–10
type of 2-azido-2-deoxygalactosyl donor.
Selenoglycoside 5
1
1
was prepared via azidophenylselenylation of the galactal, which
is a shorter process than typically used protocols for the prepara-
tion of 2-azido-2-deoxygalactosyl donors via azidonitration of
1
2
glycals.
Aspergillus fumigatus is one of the most important invasive hu-
man fungal pathogens in industrialized countries. It causes inva-
sive fungal infections with high mortality rates that remain over
50%, even when using known antifungal agents. The cell wall
exopolysaccharide galactosaminogalactan (GG) of Aspergillus
fumigatus is a major virulence factor of this human fungal patho-
gen. GG is a high-molecular-weight biopolymer with a very
complex structure consisting of α-(1→4)-linked galactose, galac-
tosamine and N-acetylgalactosamine units. It plays a major role
in the adhesion of the mycelium to abiotic and biotic substrates
and in biofilm formation. Most importantly, it has immunosup-
pressive properties that favor fungal infection. Moreover, anti-GG
antibodies have been detected in human sera, and antibodies can
easily be induced in mice hyperimmunized with purified GG.
The carbohydrate epitopes responsible for the immune function of
The di-(tert-butyl)silylidene (DTBS) group was selected to protect
O-4 and O-6 because of its steric hindrance, which disfavors the
formation of undesirable β-glycosylation products. Despite the
previous observation
-azido-2-deoxygalactosyl donors, a 3-O-benzoyl group was
applied in this work as a temporary protecting group on O-3 of the
glycosyl donor 5 because 3-benzoates offer α-stereocontrol
through remote anchimeric participation.
1
13
1
0,14
of the good efficiency of 3-O-benzylated
2
2
3
9,15–18
The synthesis of
designed donor 5 is shown in Scheme 1 and is described in the
Supporting Information.
2
–4
Several preliminary α-galactosylation experiments with donor 5
and aliphatic and monosaccharide acceptors showed that the
optimal promoter system is Me S -MeOTf, which is more con-
3
,4
2
2
8
venient than the previously used NIS-TMSOTf or Ph SO-Tf O
2
2
1
0
GG are currently unknown. Due to the structural heterogeneity of
systems, which require the use of low temperatures and produce
a substantial amount of byproducts. The glycosylation of N-(3-
trifluoroacetyl)-propanol (6a) with 5 proceeded smoothly, leading
to expected α-linked product 7. Removal of the DTBS group
(→9), followed by regioselective 6-O-benzoylation, gave desired
2,5,6
GG and especially the lack of repeating units,
the only way to
answer this question is to use a series of labeled oligosaccharides
representing different GG-related fragments as molecular probes.
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glycosyl acceptor 11 with a free OH group at C-4. Its structure
acetylgalactosamine-containing conjugates 40-45. The structures
of products 34-45 was established by a combination of 1D and 2D
NMR spectroscopy, and these data are summarized in the Sup-
porting Information.
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was confirmed by a combination of 1D and 2D NMR spectral
data. In particular, the α-configuration of the anomeric center was
assessed based on the JH1,H2 constant (3.6 Hz). The location of the
Bz-groups at O-3 and O-6 and the presence of a free OH group at
C-4 were confirmed by the characteristic low-field signals of H-3
and H-6a,b (δH3 5.43 ppm; δH6a 4.49 ppm, δH6b 4.51 ppm) and the
high-field signal of H-4 (δH4 4.37 ppm).
b
Scheme 2. Synthesis of biotinylated glycoconjugates 34-45.
Scheme 1. Synthesis of monosaccharide donor 5, acceptors 11
and 12 and carbohydrate blocks 13-19.
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a
11
Reagents and conditions: (a) Se Ph , TMSN , PhI(OAc) ,
2
2
3
2
CH Cl , -30 → -18 °C; (b) 1 M MeONa, MeOH, CH Cl ; (c)
2
2
2
2
DTBSCl , AgOTf, Py; (d) BzCl, Py; (e) 5, Me S , MeOTf, MS 4
2
2 2
Å, CH Cl (f) 40% aq. HF, Py; (g) BzCl, Py, 0 °C.
2
2
b
Reagents and conditions: (a) Pd(OH) /C, Et N, Boc O, EtOAc,
2
3
2
atm. H ; (b) 1 M MeONa, CH Cl -MeOH (1:3) then 1 M NaOH;
(c) 33, Et N, DMF, then CF COOH; (d) Ac O, Et N, MeOH.
2
2
2
The glycosylation of acceptor 11 with donor 5, removal of the
DTBS group and 6’-O-benzoylation gave disaccharide glycosyl
acceptor 13. Subjecting this compound to multiple cycles of these
reaction under similar conditions afforded the tri- (14), tetra- (15),
penta- (16) and hexasaccharide (17) glycosyl acceptors. Their
structures, particularly the location of the Bz-groups and free OH-
groups as well as the α-configuration of the anomeric centers,
were confirmed by a combination of 1D and 2D NMR spectra,
and these data are summarized in the Supporting Information.
3
3
2
3
In parallel with the above syntheses, the application of 3-
phtalimidopropanol (6b) instead of N-TFA-analogue 6a was
studied as well. The above-described chemical protocols were
used to effectively synthesize mono-, di- and tri saccharide de-
rivatives 12, 18 and 19 (Scheme 1). The latter were successfully
converted to unprotected products 27-29, identical to those ob-
tained previously using N-(3-trifluoroacetyl)-propanol as a spacer.
The elongation of the oligosaccharide chain with compound 19
was not continued because the standard procedures for the remov-
al of the O-benzoyl and N-phthaloyl protecting groups with hy-
drazine hydrate were not quantitative and were accompanied by
the formation of acylhydrazides, resulting in the presence of
contaminants in the target oligosaccharides.
The N -groups in products 11 and 13-17 were effectively reduced
3
by catalytic hydrogenation over Pd(OH) /C in the presence of
2
Boc O and Et N to produce N-Boc-protected aminogalactosides
2
3
2
1-26 (Scheme 2). Their saponification by treatment with MeONa
and aq. NaOH afforded compounds 27-32, which were then bioti-
1
9
nylated with reagent 33 via an unprotected spacer aminopropyl
group. Acid hydrolysis with TFA cleaved the N-Boc protecting
groups, affording target galactosamine-containing glycoconju-
gates 34-39. Parts of these products were N-acetylated to give N-
Biotinylated oligosaccharides 34-45, together with their analogues
possessing N-acetylated and nonacetylated GlcN units (46-49)
2
0,21
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(Figure 1), were immobilized on streptavidin-coated microtiter
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plates to form a glycoarray, which was used to analyze the speci-
ficity of anti-GG mouse mAbs G8-8, C22-3 and H6-4 as de-
scribed for the analysis of other monoclonal antibodies directed
1
toward Aspergillus polysaccharide antigens, namely, α-(1→3)-
22,23
24
glucan
and galactomannan. It was revealed that the minimal
epitope recognized with mAbs is a disaccharide consisting of two
GalNAc units with an α-(1→4)-linkage. All three MAbs inoculat-
ed with GG recognized the same epitope, indicating that it was
immunodominant in hyperimmunized mice (Figure 1).
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Figure 2. Testing the carbohydrate specificities of sera from
patient with CPA (N=25) or ABPA (N=30) or healthy controls
(
N=26) using nonacetylated conjugate 39 (A) and its N-acetylated
analogue 45 (B). Mann-Whitney test: * - significant 0.01<p<0.05;
* - very significant p<0.01.
*
Supporting Information
General methods, full experimental procedures, characterization data
1
13
for all new compounds, copies of H, C NMR and ELISA experiments
are provided in the Supporting Information. This material is available
free of charge via the Internet at http://pubs.acs.org.
Corresponding Author
nen@ioc.ac.ru
Figure 1. Assay of carbohydrate specificity of anti-GG monoclo-
nal antibodies by ELISA on a glycoarray of biotinylated gly-
coconjugates 34-47. C: control without carbohydrate ligand.
Notes
The authors declare no competing financial interests.
The preliminary assays with the glycoarray composed of biotinyl-
ated oligosaccharides 35-39 and 41-45 showed that anti-GG anti-
bodies in the sera of patients with allergic bronchopulmonary and
chronic pulmonary aspergillosis (ABPA and CPA) recognized
both N-acetylated and nonacetylated oligogalactosamines with a
degree of polymerization (dp) of at least 3 (Figure 1S). Further
elongation of oligosaccharide ligand favors its better recognition
by the serum anti-GG antibodies. Accordingly, hexasaccharides
The synthesis of biotinylated glycoconjugates and the screening
of monoclonal antibodies by glycoarray was supported by Russian
Science Foundation Grant 19-73-30017 (NEN); the analysis of the
patients sera was supported by the French Government's Inves-
tissement d'Avenir program, Laboratoire d'Excellence "Integrative
Biology of Emerging Infectious Diseases" (grant n°ANR-10-
LABX-62-IBEID) (JPL) and Agence Nationale de la Recherche
(ANR 16 CE92 0039-01 AFUINF) (JPL).
3
9 and 45 were used to further analyze the levels of anti-GG
antibodies in the sera of cohorts of patients with ABPA and CPA.
The level of antibodies that recognized these hexasaccharides was
significantly higher in the sera of aspergillosis patients than that in
the control sera (Figure 2). The difference was more pronounced
with antibodies directed against N-acetylated ligand 45 than
nonacetylated 39.
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