Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 16, 2025
We
report
here
a
new
catalytic
and
exclusively
cis-selective
glycosylation
strategy
for
multigram
scale
synthesis
of
biologically
valuable
Tn
antigens.
The
underlying
iron-catalyzed
glycal
1,2-cis-aminoglycosylation
method
is
effective
with
variety
galactosyl
donors
amino
acid
acceptors
consistently
high
stereoselectivity.
Rapid
scalable
postglycosylation
transformations
readily
afford
single
diastereomeric
antigens
in
yields.
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:
2023,
Volume and Issue:
62(18)
Published: March 7, 2023
Stereoselective
C-glycosylation
reactions
are
increasingly
gaining
attention
in
carbohydrate
chemistry
because
they
enable
glycosyl
precursors,
readily
accessible
as
anomeric
mixtures,
to
converge
a
single
diastereomeric
product.
However,
controlling
the
stereochemical
outcome
through
transition-metal
catalysis
remains
challenging,
and
methods
that
leverage
bench-stable
heteroaryl
sulfone
donors
facilitate
glycosylation
rare.
Herein,
we
show
two
complementary
nonprecious
metal
catalytic
systems,
based
on
iron
or
nickel,
which
capable
of
promoting
efficient
C-C
coupling
between
sulfones
aromatic
nucleophiles
electrophiles
distinct
mechanisms
modes
activation.
Diverse
C-aryl
glycosides
were
secured
with
excellent
selectivity,
scope,
functional-group
compatibility,
reliable
access
both
α
β
isomers
was
possible
for
key
sugar
residues.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(27), P. 7569 - 7580
Published: Jan. 1, 2023
A
novel
photoredox-catalyzed
radical
conjugate
addition
of
1,4-dihydropyridine-derived
glycosyl
esters
and
dehydroalanine
derivatives
via
anomeric
C(sp
3
)–O
bond
homolysis
to
construct
C
-glycosyl
amino
acids
peptides
is
for
the
first
time
described.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(24), P. 16753 - 16763
Published: June 11, 2024
In
the
realm
of
organic
synthesis,
catalytic
and
stereoselective
formation
C-glycosidic
bonds
is
a
pivotal
process,
bridging
carbohydrates
with
aglycones.
However,
inherent
chirality
saccharide
scaffold
often
has
substantial
impact
on
stereoinduction
imposed
by
chiral
ligand.
this
study,
we
have
established
an
unprecedented
zirconaaziridine-mediated
asymmetric
nickel
catalysis,
enabling
diastereoselective
coupling
bench-stable
glycosyl
phosphates
range
(hetero)aromatic
glycal
iodides
as
feasible
electrophiles.
Our
developed
method
showcases
broad
scope
high
tolerance
for
various
functional
groups.
More
importantly,
precise
stereocontrol
toward
both
anomeric
configurations
forming
C(sp2)-glycosides
can
be
realized
simply
utilizing
popular
bioxazoline
(biOx)
ligands
in
reductive
Ni
catalysis.
Regarding
operating
mechanism,
experimental
computational
studies
support
occurrence
redox
transmetalation
leading
to
transient,
bimetallic
Ni–Zr
species
that
acts
potent
efficient
single-electron
reductant
process.
