Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(43)
Published: July 12, 2023
Abstract
Cyclodextrins
are
widely
used
as
carriers
of
small
molecules
for
drug
delivery
owing
to
their
remarkable
host
properties
and
excellent
biocompatibility.
However,
cyclic
oligosaccharides
with
different
sizes
shapes
limited.
Cycloglycosylation
ultra‐large
bifunctional
saccharide
precursors
is
challenging
due
the
constrained
conformational
spaces.
Herein
we
report
a
promoter‐controlled
cycloglycosylation
approach
synthesis
α‐(1→6)‐linked
mannosides
up
32‐mer.
thioglycosides
(
Z
)‐ynenoates
was
found
be
highly
dependent
on
promoters.
In
particular,
sufficient
amount
gold(I)
complex
played
key
role
in
proper
preorganization
transition
state,
providing
32‐mer
polymannoside,
which
represents
largest
synthetic
polysaccharide
date.
NMR
experiments
computational
study
revealed
that
2‐mer,
4‐mer,
8‐mer,
16‐mer,
adopted
states
shapes.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(51), P. 9479 - 9484
Published: Dec. 16, 2022
Nucleoside
analogues
are
widely
used
as
anticancer
and
antiviral
drugs.
Here,
we
develop
a
highly
efficient
gold(I)-catalyzed
N-glycosylation
approach
for
versatile
synthesis
of
various
types
nucleosides
deoxynucleosides
with
glycosyl
(Z)-ynenoates
donors.
The
wide
scope
the
was
demonstrated
by
31
pyrimidine
8
purine
nucleosides.
Remarkably,
pyranosyl
purines
found
to
be
very
effective
regioselective
N9
Based
on
catalytic
approach,
convenient
two
5'-deoxynucleosides
drugs
(capecitabine
galocitabine),
four
2'-deoxynucleoside
(floxuridine,
trifluridine,
decitabine
cladribine),
3',5'-dideoxynucleoside
analogues,
2',5'-dideoxynucleoside
achieved
in
collective
manner.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(43)
Published: July 12, 2023
Cyclodextrins
are
widely
used
as
carriers
of
small
molecules
for
drug
delivery
owing
to
their
remarkable
host
properties
and
excellent
biocompatibility.
However,
cyclic
oligosaccharides
with
different
sizes
shapes
limited.
Cycloglycosylation
ultra-large
bifunctional
saccharide
precursors
is
challenging
due
the
constrained
conformational
spaces.
Herein
we
report
a
promoter-controlled
cycloglycosylation
approach
synthesis
α-(1→6)-linked
mannosides
up
32-mer.
thioglycosides
(Z)-ynenoates
was
found
be
highly
dependent
on
promoters.
In
particular,
sufficient
amount
gold(I)
complex
played
key
role
in
proper
preorganization
transition
state,
providing
32-mer
polymannoside,
which
represents
largest
synthetic
polysaccharide
date.
NMR
experiments
computational
study
revealed
that
2-mer,
4-mer,
8-mer,
16-mer,
adopted
states
shapes.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(45), P. 8381 - 8386
Published: Nov. 8, 2022
Pseudomonas
aeruginosa
is
a
leading
cause
of
urinary
tract,
pulmonary,
and
wound
infections
becoming
increasingly
resistant
to
antibiotics.
Here,
we
report
the
iodonium-
gold(I)-promoted
bimodal
glycosylation
glycosyl
(Z)-ynenoates
for
highly
β-selective
promoter-controlled
synthesis
antigenic
evaluation
series
1,2-cis-β-linked
mannuronic
acid
alginate
glycans
P.
up
24-mer,
which
represents
longest
polymannuronic
synthesized
date.
By
screening
six
synthetic
with
mouse
serum
antibodies,
identified
tetrasaccharide
as
optimal
antigen
epitope
development
vaccines
against
aeruginosa.
Advanced Science,
Journal Year:
2024,
Volume and Issue:
11(11)
Published: Jan. 15, 2024
Abstract
A
noncovalent
organocatalytic
concerted
addition
of
phenol
to
glycal
is
developed
for
the
stereoselective
and
regioselective
construction
biologically
important
phenolic
2‐deoxyglycosides,
featuring
wide
substrate
tolerance.
The
method
relies
on
an
anion‐bridged
dual
hydrogen
bond
interaction
which
experimentally
proved
by
Nuclear
Magnetic
Resonance
(NMR),
Ultraviolet
visible
(UV–vis),
fluorescence
analysis.
Experimental
evidence
including
kinetic
analysis,
Kinetic
Isotope
Effect
(KIE)
studies,
linear
free
energy
relationship,
Hammett
plot,
density
functional
theory
(DFT)
calculations
provided
a
mechanism
where
high‐energy
oxocarbenium
ion
not
formed.
In
addition,
potential
utility
this
further
demonstrated
synthesis
active
glycosylated
flavones.
benchmarking
studies
demonstrate
significant
advances
in
newly
compared
previous
approaches.
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(12), P. 2365 - 2369
Published: Jan. 1, 2024
Additive-assisted
α-selective
Kdo
glycosylation
using
a
peracetylated
ynenoate
is
described
for
stereoselective
synthesis
of
the
protected
trisaccharide
variant
relevant
to
lipopolysaccharide
Coxiella
burnetii
strain
Nine
Mile.
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(19), P. 3986 - 3994
Published: Jan. 1, 2024
Sulfated
mannuronate
glycans
with
up
to
17
sulfation
sites
were
synthesized
using
a
microwave-assisted
approach
and
evaluated
as
inhibitors
against
SARS-CoV-2.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 16, 2024
Comprehensive
Summary
Traditional
protecting
groups
are
often
removed
under
harsh
conditions
with
potentially
hazardous
reagents,
thereby
impeding
the
convenient
synthesis
of
oligosaccharides
and
glycosides.
Herein,
we
present
to
utilize
photolabile
ortho
‐nitro‐benzyl
carbonate
(
o
NBC)
as
a
permanent
hydroxyl
group
for
stereocontrolled
The
Ph
3
PO‐modulated
glycosylation
strongly
disarmed
per‐
O
‐
NBC‐protected
glycosyl
ynenoates
preferred
afford
glycosides
excellent
α‐selectivities
via
β‐phosphonium
transition
state.
Based
on
NBC‐mediated
galactosylation,
glycolipid
digalactosyl
diacylglycerol
(DGDG)
containing
six
double
bonds
two
esters
was
achieved
in
straightforward
manner.
The Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
87(5), P. 3402 - 3421
Published: Feb. 16, 2022
A
photolabile
protecting
group
(PPG)
2-(2-nitrophenyl)-propyloxycarbonyl
(NPPOC)
was
explored
in
glycosylation
and
applied
the
consecutive
synthesis
of
oligosaccharides.
NPPOC
displays
a
strong
neighboring
participation
(NGP)
effect
to
facilitate
construction
1,2-trans
glycosides
excellent
yield.
Notably,
could
be
efficiently
removed
by
photolysis,
deprotection
conditions
are
friendly
typical
groups.
branched
asymmetric
oligomannose
Man6
rapidly
prepared,
assembly
oligosaccharides
without
intermediate
purification
further
investigated
owing
compatibility
between
NPPPOC's
photolysis
glycosylation.
