Angewandte Chemie,
Год журнала:
2023,
Номер
135(43)
Опубликована: Июль 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,
Год журнала:
2023,
Номер
25(19), С. 3548 - 3552
Опубликована: Май 9, 2023
Rapid
synthesis
of
saccharides
by
a
chemical
method
is
an
efficient
way
to
meet
the
demand
for
well-defined
glycans
probe
their
biological
functions.
Herein,
feasible
and
convenient
strategy
saccharide
was
established
introducing
photosensitive
fluorous
tag
at
anomeric
position
glycosides.
The
used
not
only
in
polytetrafluoroethylene-assisted
rapid
purification
but
also
as
temporary
protecting
group
reducing
end
carbohydrates.
tag-protected
glycosides
could
be
transformed
into
new
glycosyl
donors
convergent
after
orthogonal
deprotection
photolysis.
Via
combination
β-directing
C-5
carboxylate
glycosylation
strategy,
β-1,4-mannuronates
were
efficiently
prepared.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(44), С. 8863 - 8867
Опубликована: Янв. 1, 2023
A
side-chain
anchoring
strategy
has
been
developed
as
an
effective
method
for
the
synthesis
of
C-terminal
Cys-containing
peptide
acids.
However,
application
this
to
CCAs
containing
more
than
one
disulfide
bond
is
still
hindered
due
trifluoroacetic
acid
(TFA)
lability
anchored
groups.
Herein,
we
report
a
photocleavable
using
newly
molecules
having
protecting
groups
that
are
stable
against
TFA
cleavage
assist
in
formation
bonds.
The
utility
new
was
demonstrated
by
Riparin
1.1
and
hCNP22
α-conotoxin
Vc1.1
two
This
will
provide
possibilities
disulfide-rich
Abstract
Chikusetsusaponin
IVa
butyl
ester
(CS-IVa-Be)
is
a
triterpene
saponin
that
acts
as
novel
IL6R
antagonist
for
inducing
breast
cancer
cell
apoptosis.
However,
the
structure–activity
relationship
this
class
of
saponins
remains
unclear.
Here,
we
report
gram-scale
synthesis
CS-IVa-Be
and
efficient
preparation
eight
its
analogues.
was
demonstrated
to
have
significant
antitumor
activities
against
MDA-MB-231,
HepG2,
A549
cells.
When
one
sugar
residues
at
either
3-OH
or
28-COOH
position
cleaved,
length
alkyl
chain
on
d-glucuronic
acid
residue
changed,
these
analogues
showed
varied
inhibitory
lines.
Notably,
carboxylic
form
exhibited
stronger
activity
MDA-MB-231
Furthermore,
inhibited
proliferation
in
dose-dependent
manner
by
arresting
cycle
G2/M
phase.
Chinese Journal of Chemistry,
Год журнала:
2022,
Номер
41(2), С. 151 - 158
Опубликована: Окт. 3, 2022
Comprehensive
Summary
Group
B
Streptococcus
(GBS)
is
the
major
pathogen
that
causes
invasive
infectious
diseases
in
neonates
and
infants.
The
development
of
preventive
therapeutic
strategies
against
GBS
infection
has
been
becoming
most
pressing
subject
worldwide.
carbohydrate
(GBC),
group
B‐specific
polysaccharide
distinguishes
with
other
streptococci
species,
identified
as
an
attractive
antigen
for
diagnosis
vaccine
because
its
highly
conservative
tetra‐antennary
structure.
In
this
paper,
a
convergent
[3
+
5]
glycosylation
strategy
efficient
synthesis
octasaccharide
derivative
related
to
GBC
oligosaccharide
unit
II
developed.
synthesis,
each
reaction
was
efficiently
constructed
glycosyl
imidates,
especially
trifluoroacetimidate,
donors,
glycosidic
bond
stereoselectively
controlled
via
neighboring
participation
effect
acyl
on
2‐
O
‐position
imidate
donors
or
solvent
Et
2
O.
Furthermore,
aminoethylphosphate
smoothly
installed
6‐
d
‐glucitol
residue
using
phosphoramidite
method.
After
global
deprotection,
target
successfully
obtained
from
29
steps
overall
yield
1.37%.
free
amino
spacer
molecule
enables
modification
functionalized
biomolecules
further
biological
studies.
Angewandte Chemie,
Год журнала:
2023,
Номер
135(43)
Опубликована: Июль 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.
