Angewandte Chemie,
Год журнала:
2023,
Номер
136(5)
Опубликована: Ноя. 30, 2023
Abstract
Azomethine
imines,
as
a
prominent
class
of
1,3‐dipolar
species,
hold
great
significance
and
potential
in
organic
medicinal
chemistry.
However,
the
reported
synthesis
centrally
chiral
azomethine
imines
relies
on
kinetic
resolution,
construction
axially
remains
unexplored.
Herein,
we
present
through
copper‐
or
phosphoric
acid
catalyzed
ring‐closure
reactions
N
′‐(2‐alkynylbenzylidene)hydrazides,
showcasing
high
efficiency,
mild
conditions,
broad
substrate
scope,
excellent
enantioselectivity.
Furthermore,
biological
evaluation
revealed
that
synthesized
effectively
protect
dorsal
root
ganglia
(DRG)
neurons
by
inhibiting
apoptosis
induced
oxaliplatin,
offering
promising
therapeutic
approach
for
chemotherapy‐induced
peripheral
neuropathy
(CIPN).
Remarkably,
(
S
)‐
R
)‐atropisomers
displayed
distinct
neuroprotective
activities,
underscoring
axial
stereochemistry.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(9), С. 6283 - 6293
Опубликована: Фев. 21, 2024
We
herein
introduce
biarylhemiboronic
esters
as
a
new
type
of
bridged
biaryl
reagent
for
asymmetric
synthesis
axially
chiral
structures,
and
the
palladium-catalyzed
Suzuki-Miyaura
cross-coupling
is
developed.
This
dynamic
kinetic
atroposelective
coupling
reaction
exhibits
high
enantioselectivity,
good
functional
group
tolerance,
broad
substrate
scope.
The
synthetic
application
current
method
was
demonstrated
by
transformations
product
programmed
polyarene.
Preliminary
mechanistic
studies
suggested
that
proceeded
via
an
enantio-determining
transmetalation
step.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(6), С. 1269 - 1284
Опубликована: Янв. 31, 2024
Abstract
Axially
chiral
architectures
exist
widely
in
natural
products,
biologically
relevant
molecules,
ligands
and
catalysts
as
well
functional
materials.
Therefore,
catalytic
asymmetric
synthesis
of
atropisomers
has
become
one
the
most
fast‐growing
fields
community
chemistry
rapid
advances
have
occurred.
Among
different
methods
reported,
organocatalytic
atroposelective
dynamic
kinetic
resolution
(DKR)
involving
ring
manipulations
stands
out
a
cutting‐edge
technology
to
construct
axial
chirality
from
point
atom/step
economy.
In
this
DKR
strategy,
configurational
lability
starting
materials
originates
chirally‐labile
structure
cyclic
substrates/intermediates
or
transient
formation
through
noncovalent
interactions
acyclic
substrates.
The
two
material
are
equilibrium
reaction
medium,
ensuring
constant
transformation
less
reactive
atropisomer
into
more
one,
then
single
enantiopure
product
presence
an
appropriate
organocatalyst.
This
review
summarizes
recent
advancements
on
topic,
including
their
scopes,
limitations,
mechanisms,
applications
provides
some
insights
further
developments.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(8)
Опубликована: Янв. 6, 2024
Atropisomeric
phosphines
hold
considerable
significance
in
asymmetric
catalysis,
yet
their
synthesis
presents
a
formidable
challenge
owing
to
intricate
multistep
procedures.
In
this
context,
groundbreaking
methodology
has
been
presented
for
preparation.
This
innovative
approach
entails
an
atroposelective
rhodium-catalyzed
C-H
activation
employing
aryl
and
heteroaryl
halides,
chelated
by
P(III)
center.
The
essence
of
strategy
lies
its
ability
directly
construct
chiral
phosphine
ligands
single
step,
thereby
exhibiting
exceptional
efficiency
terms
atom
redox
economy.
Illustrative
examples
serve
demonstrate
the
immense
potential
situ-formed
catalysis.
Mechanistic
experiments
have
further
provided
invaluable
insights
into
transformation.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(19), С. 9560 - 9581
Опубликована: Янв. 1, 2024
Chiral
amine
scaffolds
are
among
the
most
important
building
blocks
in
natural
products,
drug
molecules,
and
functional
materials,
which
have
prompted
chemists
to
focus
more
on
their
synthesis.
Among
accomplishments
chiral
synthesis,
transition-metal-catalyzed
enantioselective
C-N
cross-coupling
is
considered
one
of
efficient
protocols.
This
approach
combines
traditional
C(sp
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(28)
Опубликована: Май 16, 2024
Abstract
Axially
chiral
biaryl
scaffolds
are
important
in
pharmaceuticals,
natural
products,
and
asymmetric
synthesis.
Atroposelective
ring‐opening
of
configurationally
labile
reagents
via
dynamic
kinetic
transformation
provides
a
valuable
approach
to
access
axially
atropisomers.
This
review
summarizes
seminal
contributions
recent
advancements
on
this
topic
based
the
use
different
types
reagents.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(39)
Опубликована: Июнь 20, 2023
The
development
of
catalytic
asymmetric
reaction
with
water
as
the
reactant
is
challenging
due
to
reactivity-
and
stereoselectivity-control
issues
resulted
from
low
nucleophilicity
small
size
water.
We
disclose
herein
a
chiral
phosphoric
acid
(CPA)
catalyzed
atroposelective
ring-opening
biaryl
oxazepines
A
series
undergo
CPA
hydrolysis
in
highly
enantioselective
manner.
key
for
success
this
use
new
SPINOL-derived
catalyst
high
reactivity
oxazepine
substrates
towards
under
acidic
conditions.
Density
functional
theory
calculations
suggest
that
proceeds
via
dynamic
kinetic
resolution
pathway
addition
imine
group
both
enantio-
rate-determining.
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 2927 - 2938
Опубликована: Фев. 4, 2025
Cyclic
aryliodoniums
are
widely
used
as
arylative
reagents
via
a
ring
opening
process.
Despite
the
numerous
synthetic
achievements,
precise
control
of
regioselective
unsymmetrical
cyclic
remains
fundamental
challenge
in
chemistry.
Herein,
we
report
an
effective
substrate
and
catalyst
cocontrolled
chemoselective
reclosing
with
alkynes.
Particularly,
ortho-installed
aryliodonium
amido
groups
palladium
catalysts
direct
switch
formation
either
C–N
or
C–O
bond
during
annulation.
The
experiment
density
functional
theory
(DFT)
study
indicate
cooperative
mode
influenced
by
steric
electronic
effects
substrates
catalysts.
This
method
features
broad
scope,
good
compatibility,
high
chemoselectivity,
providing
divergent
tetra-heterocyclic
arenes.
It
further
demonstrated
practicality
this
protocol
complex
derived
from
series
clinical
drugs
efficiency.
We
report
a
one-pot,
three-component
synthesis
of
dibenzophosphole
under
mild
conditions,
facilitated
by
copper–silver
bimetallic
system.
This
method
employs
readily
available
cyclic
diaryliodonium
salts
as
arylation
reagents
and
sodium
phosphaethynolate
(NaOCP)
phosphorus
source,
eliminating
the
need
for
lithium
energy-intensive
chlorophosphines.
The
resulting
derivatives
exhibit
strong
fluorescence,
highlighting
their
potential
fluorescent
materials.
Abstract
Heteroaromatic
N
‐oxides,
renowned
for
their
highly
polar
N─O
bond
and
robust
structure,
exhibit
significant
bioactivities
have
played
a
pivotal
role
in
various
drug
development
projects
since
the
discovery
of
Minoxidil.
Moreover,
heteroaromatic
featuring
axially
chiral
biaryl
frameworks,
are
indispensable
as
Lewis
base
catalysts
ligands
organic
synthesis.
Despite
importance,
synthesizing
these
compounds
is
challenging,
necessitating
starting
materials
or
resolution
processes.
Catalytic
strategies
rely
on
functionalization
‐oxide
compounds,
leading
to
products
with
relatively
limited
skeletal
diversity.
This
study
introduces
Cu‐catalyzed
atroposelective
method
‐oxides
via
de
novo
ring
formation.
mild
efficient
approach
achieves
excellent
stereoselectivities
(up
99:1
er),
enabling
production
wide
array
novel
scaffolds.
The
product
3f
demonstrates
high
stereoselectivity
recyclability
catalyst.
Additionally,
3e
exhibits
promising
therapeutic
efficacy
against
triple‐negative
breast
cancer,
IC
50
values
4.8
5.2
µ
m
MDA‐MB‐231
MDA‐MB‐468
cells,
respectively.
research
not
only
advances
synthesis
challenging
but
also
encourages
further
exploration
entities
bioactive
small
molecules.
