Abstract
The
first
total
synthesis
of
capsular
polysaccharide
(CPS)
repeating
unit
[2)‐α‐
l
‐Rhap‐1→P→4‐β‐
d
‐ManpNAc‐(1→4)‐α‐
‐Glcp‐(1]
n
streptococcus
suis
serotype
8
is
reported.
key
features
the
are
formation
1,2
cis
glycosidic
linkage
between
mannosamine
and
glucose
derived
monomers
to
get
disaccharide
which
on
coupling
with
rhamnose
H‐phosphonate
followed
by
oxidation
P−H
bond
global
debenzylation
provide
targeted
trisaccharide
8.
Chemical Reviews,
Год журнала:
2023,
Номер
123(10), С. 6793 - 6838
Опубликована: Апрель 26, 2023
Carbohydrates
are
a
fundamental
unit
playing
pivotal
roles
in
all
the
biological
processes.
It
is
thus
essential
to
develop
methods
for
synthesizing,
functionalizing,
and
manipulating
carbohydrates
further
understanding
of
their
functions
creation
sugar-based
functional
materials.
is,
however,
not
trivial
such
methods,
since
densely
decorated
with
polar
similarly
reactive
hydroxy
groups
stereodefined
manner.
New
approaches
chemo-
site-selective
transformations
are,
therefore,
great
significance
revolutionizing
sugar
chemistry
enable
easier
access
sugars
interest.
This
review
begins
brief
overview
innate
reactivity
carbohydrates.
followed
by
discussions
about
catalytic
enhance,
override,
or
be
orthogonal
transformation
avoids
making
list
reactions,
but
rather
focuses
on
summarizing
concept
behind
each
reported
transformation.
The
literature
references
were
sorted
into
sections
based
underlying
ideas
approaches,
which
we
hope
will
help
readers
have
better
sense
current
state
innovative
field.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 2, 2025
Acylation
stands
as
a
fundamental
process
in
both
biological
pathways
and
synthetic
chemical
reactions,
with
acylated
saccharides
their
derivatives
holding
diverse
applications
ranging
from
bioactive
agents
to
building
blocks.
A
longstanding
objective
organic
synthesis
has
been
the
site-selective
acylation
of
without
extensive
pre-protection
alcohol
units.
In
this
study,
we
demonstrate
that
by
simply
altering
chirality
N-heterocyclic
carbene
(NHC)
catalysts,
site-selectivity
saccharide
reactions
can
be
effectively
modulated.
Our
investigation
reveals
intriguing
selectivity
shift
stems
combination
factors,
including
match/mismatch
inter-
/
intramolecular
hydrogen
bonding
between
NHC
catalyst
substrates.
These
findings
provide
valuable
insights
into
design
reaction
engineering,
highlighting
potential
glycoside
analysis,
such
fluorescent
labelling,
α/β
identification,
orthogonal
selective
late-stage
modifications.
The
units
synthesis.
Here,
authors
Chemical Reviews,
Год журнала:
2024,
Номер
124(10), С. 6643 - 6689
Опубликована: Май 9, 2024
1,1′-Bi-2-naphthol
(BINOL)
has
been
extensively
used
as
the
chirality
source
in
fields
of
molecular
recognition,
asymmetric
synthesis,
and
materials
science.
The
direct
electrophilic
substitution
at
aromatic
rings
optically
active
BINOL
developed
one
most
convenient
strategies
to
structurally
modify
for
diverse
applications.
High
regioselectivity
achieved
reaction
with
electrophiles.
Depending
upon
conditions
patterns,
various
functional
groups
can
be
introduced
specific
positions,
such
6-,
5-,
4-,
3-positions,
BINOL.
Ortho-lithiation
3-position
directed
by
2-position
have
prepare
3-
3,3′-substituted
BINOLs.
use
transition
metal-catalyzed
C–H
activation
also
explored
functionalize
3-,
7-positions.
These
regioselective
substitutions
allowed
construction
tremendous
amount
derivatives
fascinating
structures
properties
reviewed
this
article.
Examples
applications
BINOLs
varying
catalysis,
chiral
sensing
are
provided.
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 18, 2025
Chiral
phosphoric
acids
(CPAs)
have
emerged
as
highly
effective
Brønsted
acid
catalysts
in
an
expanding
range
of
asymmetric
transformations,
often
through
novel
multifunctional
substrate
activation
modes.
Versatile
and
broadly
appealing,
these
benefit
from
modular
tunable
structures,
compatibility
with
additives.
Given
the
unique
types
noncovalent
interactions
(NCIs)
that
can
be
established
between
CPAs
various
reactants─such
hydrogen
bonding,
aromatic
interactions,
van
der
Waals
forces─it
is
unsurprising
catalyst
systems
become
a
promising
approach
for
accessing
diverse
chiral
product
outcomes.
This
review
aims
to
provide
in-depth
exploration
mechanisms
by
which
impart
stereoselectivity,
positioning
NCIs
central
feature
connects
broad
spectrum
catalytic
reactions.
Spanning
literature
2004
2024,
it
covers
nucleophilic
additions,
radical
atroposelective
bond
formations,
highlighting
applicability
CPA
organocatalysis.
Special
emphasis
placed
on
structural
mechanistic
features
govern
CPA-substrate
well
tools
techniques
developed
enhance
our
understanding
their
behavior.
In
addition
emphasizing
details
stereocontrolling
elements
individual
reactions,
we
carefully
structured
this
natural
progression
specifics
broader,
class-level
perspective.
Overall,
findings
underscore
critical
role
catalysis
significant
contributions
advancing
synthesis.
Organic Letters,
Год журнала:
2022,
Номер
24(12), С. 2294 - 2298
Опубликована: Март 17, 2022
This
manuscript
describes
the
electrochemical
synthesis
of
17
different
glycosyl
fluorides
in
73-98%
yields
on
up
to
a
5
g
scale
that
relies
use
SF6
as
an
inexpensive
and
safe
fluorinating
agent.
Cyclic
voltammetry
related
mechanistic
studies
carried
out
subsequently
suggest
active
species
generated
through
cathodic
reduction
are
transient
under
these
reductive
conditions
sulfur
fluoride
byproducts
effectively
scavenged
by
Zn(II)
generate
benign
salts.
Nature Chemistry,
Год журнала:
2022,
Номер
15(3), С. 424 - 435
Опубликована: Дек. 30, 2022
Abstract
Site-selective
functionalization
is
a
core
synthetic
strategy
that
has
broad
implications
in
organic
synthesis.
Particularly,
exploiting
chiral
catalysis
to
control
site
selectivity
complex
carbohydrate
functionalizations
emerged
as
leading
method
unravel
unprecedented
routes
into
biologically
relevant
glycosides.
However,
robust
catalytic
systems
available
overcome
multiple
facets
of
stereoselectivity
challenges
this
end
still
remain
scarce.
Here
we
report
synergistic
Rh(I)-
and
organoboron-catalysed
protocol,
which
enables
access
synthetically
challenging
but
arylnaphthalene
Our
depicts
the
employment
Rh(I)
site-selective
showcases
utility
boronic
acid
compatible
co-catalyst.
Crucial
success
our
judicious
choice
suitable
organoboron
catalyst.
We
also
determine
exquisite
aspects
stereocontrol,
including
enantio-,
diastereo-,
regio-
anomeric
dynamic
kinetic
resolution,
are
concomitantly
operative.
Synthesis,
Год журнала:
2023,
Номер
55(15), С. 2361 - 2369
Опубликована: Май 3, 2023
Abstract
This
manuscript
describes
transfer
hydrogenation
of
bicyclic
nitrogen-containing
heterocyclic
compounds
using
the
immobilized
chiral
phosphoric
acid
catalyst
(R)-PS-AdTRIP
in
batch
and
continuous
flow.
A
significant
improvement
enantioselectivities
is
achieved
flow
with
a
fluidized
bed
reactor
packed
when
rate
increased
from
0.2
mL/min
to
2.0–2.5
mL/min.
The
optimized
conditions
consistently
provide
4–6%
ee
higher
selectivity
than
2
mol%
(R)-PS-AdTRIP,
are
used
generate
multiple
products
same
reactor.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(21)
Опубликована: Март 26, 2024
Abstract
Herein,
we
demonstrate
the
robustness
of
a
synergistic
chiral
Pd/organoboron
system
in
tackling
challenging
suite
site‐,
regio‐,
enantio‐
and
diastereoselectivity
issues
across
considerable
palette
biologically
relevant
carbohydrate
polyols,
when
prochiral
alkoxyallenes
were
employed
as
electrophiles.
In
view
burgeoning
role
noncovalent
interactions
(NCIs)
stereoselective
synthesis,
our
mechanistic
experiments
DFT
modeling
reaction
path
unexpectedly
revealed
that
NCIs
such
hydrogen
bonding
CH‐π
between
resting
states
Pd‐π‐allyl
complex
borinate
saccharide
are
critically
involved
stereoselectivity
control.
Our
strategy
thus
illuminates
untapped
potential
harnessing
context
transition
metal
catalysis
to
tackle
challenges
functionalization.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(21)
Опубликована: Март 26, 2024
Abstract
Herein,
we
demonstrate
the
robustness
of
a
synergistic
chiral
Pd/organoboron
system
in
tackling
challenging
suite
site‐,
regio‐,
enantio‐
and
diastereoselectivity
issues
across
considerable
palette
biologically
relevant
carbohydrate
polyols,
when
prochiral
alkoxyallenes
were
employed
as
electrophiles.
In
view
burgeoning
role
noncovalent
interactions
(NCIs)
stereoselective
synthesis,
our
mechanistic
experiments
DFT
modeling
reaction
path
unexpectedly
revealed
that
NCIs
such
hydrogen
bonding
CH‐π
between
resting
states
Pd‐π‐allyl
complex
borinate
saccharide
are
critically
involved
stereoselectivity
control.
Our
strategy
thus
illuminates
untapped
potential
harnessing
context
transition
metal
catalysis
to
tackle
challenges
functionalization.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(26), С. 17629 - 17635
Опубликована: Июнь 23, 2024
The
total
synthesis
and
structural
elucidation
of
the
antimicrobial
sactipeptide
enteropeptin
A
is
reported.
Enteropeptin
contains
a
thioaminoketal
group
with
an
unassigned
stereochemical
configuration
that
embedded
in
highly
unusual
thiomorpholine
ring.
In
this
synthesis,
linear
peptide
containing
dehydroamino
acid
pendant
cysteine
residue
subjected
to
Markovnikov
hydrothiolation
by
dithiophosphoric
catalyst.
This
cyclization
reaction
forms
central
ring
found
enteropeptins.
Both
diastereomers
at
stereocenter
were
prepared,
their
comparison
authentic
standard
allowed
for
unambiguous
assignment
natural
product
be
D
configuration.
inaugural
represents
first
reported
date.
Moreover,
strategy
disclosed
herein
serves
as
general
platform
stereochemically
defined
thiomorpholine-containing
peptides,
which
may
enable
discovery
new
cyclic
antibiotics.