Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
29(6)
Published: Nov. 8, 2022
Metabolically
stable
C-glycosides
are
an
essential
family
of
compounds
in
bioactive
natural
products,
therapeutic
agents,
and
biological
probes.
For
their
application,
development
synthetic
methods
by
connecting
glycosides
aglycons
with
strict
stereocontrol
at
the
anomeric
carbon,
as
well
high
functional-group
compatibility
environmental
is
a
pivotal
issue.
Although
Suzuki-Miyaura-type
C(sp3
)-C(sp2
)
cross-coupling
using
glycosyl
boronates
potential
candidate
for
construction
C-glycosides,
neither
itself
nor
facile
synthesis
coupling
precursor,
boronates,
have
been
achieved
to
date.
Herein,
it
was
succeeded
develop
copper-catalyzed
stereoselective
one-step
borylation
bromides
palladium-catalyzed
stereospecific
β-glycosyl
borates
aryl
give
β-C-glycosides,
which
β-configuration
carbon
trifluoroborates
stereoretentively
transferred
that
resulting
C-glycosides.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(38)
Published: June 7, 2023
Glycosyl
radical
functionalization
is
one
of
the
central
topics
in
synthetic
carbohydrate
chemistry.
Recent
advances
metal-catalyzed
cross-coupling
chemistry
and
metallaphotoredox
catalysis
provided
powerful
platforms
for
glycosyl
diversification.
In
particular,
discovery
new
precursors
conjunction
with
these
advanced
reaction
technologies
have
significantly
expanded
space
compound
synthesis.
this
Review,
we
highlight
most
recent
progress
area
starting
from
2021,
reports
included
will
be
categorized
based
on
different
types
better
clarity.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(4), P. 1204 - 1236
Published: Jan. 1, 2024
This
review
article
highlights
the
diverse
ways
in
which
recent
developments
areas
of
photocatalysis
and
visible
light
photochemistry
are
impacting
synthetic
carbohydrate
chemistry.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(24)
Published: March 22, 2022
The
glycosylative
modification
of
peptides
could
improve
the
pharmacological
properties
peptide
drugs
and
deliver
them
efficiently
to
target
sites.
Compared
with
O-/N-glycosides,
C-glycosides
exhibit
more
metabolic
stability.
We
here
disclose
first
example
visible-light-promoted
Cu-catalyzed
stereoselective
C-glycosylation.
mild
reaction
conditions
are
compatible
various
carbohydrate
substrates,
as
demonstrated
a
series
monosaccharides
disaccharide,
amenable
synthesis
wide
variety
C-glycoamino
acids
C-glycopeptidomimetics
good
yields
excellent
stereoselectivities.
dual-functional
photocatalyst
formed
in
situ
via
coordination
glycine
derivative
chiral
phosphine
Cu
complex
not
only
catalyze
photoredox
process
but
also
control
stereoselectivity
glycosylation
reaction.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(16)
Published: Feb. 10, 2023
We
herein
report
a
method
that
enables
the
generation
of
glycosyl
radicals
under
highly
acidic
conditions.
Key
to
success
is
design
and
use
sulfinates
as
radical
precursors,
which
are
bench-stable
solids
can
be
readily
prepared
from
commercial
starting
materials.
This
development
allows
installation
units
onto
pyridine
rings
directly
by
Minisci
reaction.
further
demonstrate
utility
this
in
late-stage
modification
complex
drug
molecules,
including
anticancer
agent
camptothecin.
Experimental
studies
provide
insight
into
reaction
mechanism.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(17), P. 2217 - 2236
Published: April 13, 2023
Comprehensive
Summary
C‐Glycosides
are
critical,
naturally
occurring
products
and
medicinal
candidates,
extensive
efforts
have
been
made
to
explore
efficient
approaches
for
creating
C‐glycosidic
bonds.
Transition‐metal‐catalysis,
particularly
nickel‐catalyzed
C‐glycosylation
reactions
constitute
a
promising
strategy.
However,
achieving
stereoselective
synthesis
of
α‐
β‐C‐glycosides
has
long‐standing
challenge.
To
address
this
problem,
variety
nickel‐mediated
strategies
developed.
This
review
highlights
recent
developments
in
the
diastereoselective
briefly
summarizes
mechanistic
understandings
these
methods.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(46)
Published: Sept. 27, 2022
C-Acyl
glycosides
are
versatile
intermediates
to
natural
products
and
medicinally
relevant
entities.
Conventional
cross-coupling
strategies
secure
these
molecules
often
relied
on
two-component
manifolds
in
which
a
glycosyl
precursor
is
coupled
with
an
acyl
donor
(pre-synthesized
or
generated
situ)
under
transition
metal
dual
catalysis
forge
C-C
bond.
Here,
we
disclose
three-component
Ni-catalyzed
reductive
regime
that
facilitates
the
chemoselective
union
of
halides,
organoiodides
commercially
available
isobutyl
chloroformate
as
CO
surrogate.
The
method
tolerates
multiple
functionalities
resulting
obtained
high
diastereoselectivities.
Theoretical
calculations
provide
mechanistic
rationale
for
unexpectedly
chemoselectivity
sequential
cross-electrophile
couplings.
This
approach
enables
expeditious
assembly
difficult-to-synthesize
C-acyl
glycosides,
well
late-stage
keto-glycosylation
oligopeptides.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(17), P. 2818 - 2849
Published: July 7, 2023
Abstract
In
the
last
fifteen
years,
development
of
visible‐light
photocatalysis,
metal/photoredox
dual
catalysis
has
become
forefront
as
a
new
paradigm
in
organic
synthesis
well
carbohydrate
chemistry.
It
led
to
discovery
unprecedented
transformations
and
also
improvement
known
reactions
under
mild
conditions,
employing
simple
household
light
sources
bench‐stable
precursors,
which
meet
requirements
green
chemistry
sustainable
excellent
yield
stereocontrol.
general
sense,
exploitation
photoredox
hinges
on
capability
photocatalyst
or
redox
mediator
transform
visible
into
chemical
energy
via
photo‐irradiated
SET
(single
electron
transfer),
PET
(photoinduced
HAT
(hydrogen
atom
XAT
(halogen
transfer)
potentially
unlock
unique
reaction
pathways,
thereby
generating
diverse
array
reactive
intermediates.
view
type,
mechanism,
status,
this
review
will
systematically
summarize
latest
advances
visible‐light‐promoted
photocatalytic
glycosylation
reactions,
are
driven
by
single
photoactivity
donor‐acceptor
(EDA)
complexes.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(25), P. 4519 - 4523
Published: June 22, 2022
Herein,
a
practical
and
highly
efficient
method
for
visible-light-induced
copper-catalyzed
N-aminoquinoline-directed
asymmetric
C(sp3)-C(sp3)-H
glycosylation
was
reported.
At
the
same
time,
of
nondeoxysugars
with
amino
acids
to
construct
C-glycopeptides
achieved.
This
approach
promoted
synthesis
various
provided
new
model
C-glycoamino
acids.
