Synthesis,
Год журнала:
2023,
Номер
56(07), С. 1183 - 1199
Опубликована: Окт. 17, 2023
Abstract
The
glycosylation
reaction
is
one
of
the
important
aspects
carbohydrate
chemistry,
where
two
different
units
are
frequently
linked
through
C–O
bonds.
In
pursuit
advancing
this
field,
design
and
development
sustainable
catalytic
methods
for
O-glycosylation,
which
can
provide
an
alternate
effective
tool
to
traditional
protocols
involving
stoichiometric
promoters
classical
donors,
considered
as
highly
challenging,
yet
facets
glycochemistry.
Herein,
we
report
a
simple
efficient
Fe(III)-catalyzed
method
O-glycosylation
activation
bifunctional
phenylpropiolate
glycoside
(PPG)
donors.
This
mild
involves
use
inexpensive
less
toxic
FeCl3
catalyst
easily
synthesizable,
benchtop-stable
glycosyl
ester-based
PPG
react
with
various
sugar
well
non-sugar-based
acceptors
deliver
corresponding
O-glycosides
in
good
yields
moderate
anomeric
selectivity,
along
regeneration
separable
phenylpropiolic
acid.
Importantly,
d-mannose
l-rhamnose-based
donors
afforded
high
α-anomeric
selectivity.
conditions
were
further
explored
synthesis
trisaccharides.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(16), С. 11735 - 11747
Опубликована: Авг. 1, 2023
Borate
esters
have
been
applied
widely
as
coupling
partners
in
organic
synthesis.
However,
the
direct
utilization
of
borate
acceptors
O-glycosylation
with
glycal
donors
remains
underexplored.
Herein,
we
describe
a
novel
resulting
formation
2,3-unsaturated
O-glycosides
and
2-deoxy
mediated
by
palladium
copper
catalysis,
respectively.
This
method
tolerated
broad
scope
trialkyl/triaryl
borates
various
glycals
exclusive
stereoselectivities
high
yields.
All
desired
aliphatic/aromatic
were
generated
successfully,
without
hemiacetal
byproducts
O→C
rearrangement
because
nature
esters.
The
utility
this
strategy
was
demonstrated
functionalizing
glycoside
products
to
form
saturated
β-O-glycosides,
2,3-deoxy
O-glycosides,
2,3-epoxy
O-glycosides.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(18), С. 13030 - 13041
Опубликована: Авг. 30, 2023
A
novel
highly
regio-
and
diastereoselective
phosphine-catalyzed
[2
+
4]
annulation
of
benzofuran-derived
azadienes
(BDAs)
with
acidic
hydrogen-tethered
allyl
carbonates
has
been
developed
ingeniously.
range
functionalized
spiro[benzofuran-cyclohexane]
derivatives
two
consecutive
stereocenters
were
smoothly
obtained
in
moderate
to
excellent
yields
under
mild
reaction
conditions
from
readily
available
materials.
Moreover,
this
method
is
a
practical
scalable
strategy
that
creates
the
core
structural
motif
fungistatic
drug,
griseofulvin.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(5), С. 1144 - 1151
Опубликована: Янв. 6, 2024
Abstract
We
report
a
strategy
for
stereoselective
O‐aryl‐glycoside
synthesis
by
copper‐catalyzed
cross‐coupling
of
variety
anomeric
sugars
and
(hetero)aromatic
iodides.
Stereocontrol
the
α/β
selectivity
can
be
successfully
realized
slight
structural
modifications
oxalic
diamide
ligands.
Mechanistic
studies
indicated
dynamic
kinetic
resolution
(DKR)
reaction
mechanism
controlled
ligand
structures.
This
could
performed
on
gram
scale,
has
also
been
applied
to
some
natural
products.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(12), С. 8815 - 8827
Опубликована: Июнь 5, 2024
S-Glycosides
are
more
resistant
to
enzymatic
and
chemical
hydrolysis
exhibit
higher
metabolic
stability
than
common
O-glycosides,
demonstrating
their
widespread
application
in
biological
research
drug
development.
In
particular,
β-S-glycosides
used
as
antirheumatic,
anticancer,
antidiabetic
drugs
clinical
practice.
However,
the
stereoselective
synthesis
of
is
still
highly
challenging.
Herein,
we
report
an
effective
β-S-glycosylation
using
3-O-trichloroacetimidoyl
glycal
thiols
under
mild
conditions.
The
C3-imidate
designed
guide
Pd
form
a
complex
with
glucal
from
upper
face,
followed
by
Pd–S
(thiols)
coordination
realize
β-stereoselectivity.
This
method
demonstrates
excellent
compatibility
broad
scope
various
thiol
acceptors
donors
yields
up
87%
β/α
ratio
20:1.
present
strategy
for
late-stage
functionalization
drugs/natural
products
such
estrone,
zingerone,
thymol.
Overall,
this
novel
simple
operation
approach
provides
general
practical
construction
β-thioglycosides,
which
holds
high
potential
discovery
The Chemical Record,
Год журнала:
2024,
Номер
24(9)
Опубликована: Авг. 21, 2024
Pd-catalyzed
stereoselective
glycosylations
using
unsaturated
sugar
derivatives,
glycals,
have
been
successfully
achieved
in
recent
years.
This
review
focuses
on
approaches
to
control
the
stereoselectivities
of
glycosides
via
π-allyl
intermediates
that
mimic
Tsuji-Trost
asymmetric
allylic
alkylation
reactions,
enabling
stereoselectivity
through
rational
design.
In
reaction
process,
zwitterionic
Pd-π-allyl
complexes,
formed
after
oxidative
addition
and
decarboxylation,
play
a
crucial
role
increasing
reactivities
enhancing
α-
β-glycosides.
We
summarized
recently
developed
type
3,4-carbonate
galactals,
featuring
high
efficiency,
exclusive
stereoselectivities,
broad
scope
including
O-,
N-,
S-,
C-glycosylations.
Chinese Journal of Organic Chemistry,
Год журнала:
2023,
Номер
43(9), С. 3216 - 3216
Опубликована: Янв. 1, 2023
C-Glycosides
have
attracted
more
and
attention
in
the
field
of
medicine
biology
due
to
their
excellent
physiological
activities
stability
hydrolysis/enzymolysis.However,
challenges
stereoselective
control
are
still
high
during
synthesis
process.In
this
paper,
a
method
for
preparing
β-C-glycosides
with
stereoselectivity
through
reaction
3,4-O-carbonate-D-galactal
nitroalkane
Pd(acac)2
1,4-bis(diphenylphosphino)butane
(DPPB)
ligand
at
room
temperature
has
been
reported.The
structures
target
compounds
determined
by
nuclear
magnetic
resonance
spectroscopy
(NMR),
high-resolution
mass
spectra
(HRMS)
X-ray
single
crystal
diffraction.The
wide
range
substrates,
good
compatibility
both
electron-withdrawing
electron-donating
nitroalkanes.Single
were
obtained
yields,
which
provide
reliable
rapid
construction
C-glycoside
libraries.
Abstract
Carbohydrates
and
their
conjugates
play
important
roles
in
life
activities
drug
development.
Our
group
was
committed
to
the
general
effective
glycosylation
methods
application
chemical
biology
using
unsaturated
glycosyl
donors.
In
past
five
years,
we
have
reported
several
synthetic
strategies
with
high
stereoselectivity
milder
conditions
compared
previous
works.
particular,
chemo-/regio-
stereoselective
O-glycosylation,
C-glycosylation
S-glycosylation
could
be
achieved
via
palladium
catalysis
under
open-air
at
room
temperature.
this
Account,
will
introduce
our
research
progress
constructing
four
types
of
glycosides.
1
Introduction
2
Stereoselective
Synthesis
O-Glycosides
3
C-Glycosides
4
N-Glycosides
5
S-Glycosides
6
Conclusion
Molecules,
Год журнала:
2024,
Номер
29(19), С. 4710 - 4710
Опубликована: Окт. 4, 2024
An
efficient
and
versatile
glycosylation
methodology
is
crucial
for
the
systematic
synthesis
of
oligosaccharides
glycoconjugates.
A
direct
intermolecular
an
indirect
intramolecular
have
been
developed,
former
can
be
applied
to
medium-to-long-chain
glycans
like
that
nucleotides
peptides.
The
development
a
generally
applicable
approach
stereoselective
construction
glycosidic
bonds
remains
major
challenge,
especially
1,2-
