Angewandte Chemie,
Год журнала:
2024,
Номер
136(30)
Опубликована: Май 15, 2024
Abstract
Atropisomers
hold
significant
fascination,
not
only
for
their
prevalence
in
natural
compounds
but
also
biological
importance
and
wide‐ranging
applications
as
chiral
materials,
ligands,
organocatalysts.
While
biaryl
heterobiaryl
atropisomers
are
commonly
studied,
the
enantioselective
synthesis
of
less
abundant
heteroatom‐linked
non‐biaryl
presents
a
formidable
challenge
modern
organic
synthesis.
Unlike
classical
atropisomers,
these
molecules
allow
rotation
around
two
bonds,
resulting
low
barriers
to
enantiomerization
through
concerted
bond
rotations.
In
recent
years
discovery
new
configurationally
stable
rare
scaffolds
such
aryl
amines,
ethers
sulfones
well
innovative
methodologies
control
configuration
have
been
disclosed
literature
constitute
topic
this
minireview.
ACS Catalysis,
Год журнала:
2024,
Номер
14(5), С. 3475 - 3481
Опубликована: Фев. 21, 2024
Diaryl
ethers
are
important
structural
motifs
widely
found
in
bioactive
natural
products,
ligands,
and
catalysts.
While
there
a
variety
of
methods
available
to
generate
diaryl
ethers,
progress
on
the
construction
axially
chiral
has
been
slow.
We
report
herein
an
atroposelective
copper-catalyzed
cycloaddition
between
bisalkynes
azides.
With
indane-fused
BOX
ligand
used,
diverse
array
C–O
atropisomers
obtained
with
up
97%
yield
99%
ee.
Control
experiments
showed
that
sequential
enantioselective
desymmetrization–kinetic
resolution
process
is
involved,
former
plays
major
role.
In
addition,
asymmetric
depletion
observed
for
this
catalytic
synthesis
by
nonlinear
effect
studies.
By
thermal
racemization
experiments,
rotational
barrier
axis
3aa
calculated
be
35.9
kcal/mol,
which
lays
foundation
its
isolation,
as
well
further
applications.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(30)
Опубликована: Май 15, 2024
Atropisomers
hold
significant
fascination,
not
only
for
their
prevalence
in
natural
compounds
but
also
biological
importance
and
wide-ranging
applications
as
chiral
materials,
ligands,
organocatalysts.
While
biaryl
heterobiaryl
atropisomers
are
commonly
studied,
the
enantioselective
synthesis
of
less
abundant
heteroatom-linked
non-biaryl
presents
a
formidable
challenge
modern
organic
synthesis.
Unlike
classical
atropisomers,
these
molecules
allow
rotation
around
two
bonds,
resulting
low
barriers
to
enantiomerization
through
concerted
bond
rotations.
In
recent
years
discovery
new
configurationally
stable
rare
scaffolds
such
aryl
amines,
ethers
sulfones
well
innovative
methodologies
control
configuration
have
been
disclosed
literature
constitute
topic
this
minireview.
Chirality
plays
a
crucial
role
in
the
pharmacological
activity
of
triazoles,
key
scaffold
antifungal
agents
and
various
therapeutic
applications.
This
study
focuses
on
optimizing
enantiomeric
resolution
chiral
triazoles
using
supercritical
fluid
chromatography
(SFC)
10
different
columns,
either
immobilized
or
coated,
chlorinated
nonchlorinated,
cellulose
amylose-based
stationary
phases
(CSPs).
Four
novel
two
marketed
ones
(tebuconazole
hexaconazole)
were
separated
to
determine
optimal
conditions.
The
best
was
achieved
CSPs
across
tested
compounds.
Optical
rotation
X-ray
crystallography
employed
absolute
configurations
purified
enantiomers.
Chemical Science,
Год журнала:
2024,
Номер
15(16), С. 5993 - 6001
Опубликована: Янв. 1, 2024
Axially
chiral
molecular
scaffolds
are
widely
present
in
therapeutic
agents,
natural
products,
catalysts,
and
advanced
materials.
The
construction
of
such
molecules
has
garnered
significant
attention
from
academia
industry.
catalytic
asymmetric
synthesis
axially
biaryls,
along
with
other
non-biaryl
molecules,
been
extensively
explored
the
past
decade.
However,
atroposelective
C-O
axial
chirality
remains
largely
underdeveloped.
Herein,
we
document
a
copper-catalyzed
compounds
using
novel
1,8-naphthyridine-based
ligands.
Mechanistic
investigations
have
provided
good
evidence
support
mechanism
involving
synergistic
interplay
between
desymmetrization
reaction
kinetic
resolution
process.
method
described
this
study
holds
great
significance
for
compounds,
promising
applications
organic
chemistry.
utilization
ligands
copper
catalysis
is
anticipated
to
find
broad
copper(i)-catalyzed
azide-alkyne
cycloadditions
(CuAACs)
beyond.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июнь 10, 2024
Chiral
1,2,3-triazoles
are
highly
attractive
motifs
in
various
fields.
However,
achieving
catalytic
asymmetric
click
reactions
of
azides
and
alkynes
for
chiral
triazole
synthesis
remains
a
significant
challenge,
mainly
due
to
the
limited
systems
substrate
scope.
Herein,
we
report
an
enantioselective
azidation/click
cascade
reaction
N-propargyl-β-ketoamides
with
readily
available
potent
azido
transfer
reagent
via
copper
catalysis,
which
affords
variety
up
99%
yield
95%
ee
under
mild
conditions.
Notably,
1,5-disubstituted
triazoles
that
have
not
been
accessed
by
previous
also
prepared
good
functional
group
tolerance.
Organic Letters,
Год журнала:
2023,
Номер
25(24), С. 4504 - 4509
Опубликована: Июнь 9, 2023
The
synthesis
of
chiral
triazole-fused
pyrazine
scaffolds
from
readily
available
substrates
in
a
step-economical
asymmetric
catalytic
way
is
highly
appealing.
We
herein
report
that
an
efficient
Cu/Ag
relay
catalyzed
protocol
employing
cascade
propargylic
amination,
hydroazidation,
and
[3
+
2]
cycloaddition
reaction
with
high
efficiency
to
access
the
target
enantioenriched
1,2,3-triazolo[1,5-a]pyrazine
has
been
accomplished
by
applying
novel
N,N,P-ligand.
one-pot
three
components
exhibits
functional
group
tolerance,
excellent
enantioselectivities,
broad
substrate
scope
starting
materials.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(23), С. 6819 - 6849
Опубликована: Янв. 1, 2024
This
review
highlights
recent
advances
in
the
atroposelective
preparation
of
axially
chiral
azole
derivatives,
emphasizing
mechanistic
insights
and
synthetic
applications
development
this
class
five-membered
heterocyclic
frameworks.
Angewandte Chemie International Edition,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 11, 2025
Pillar[n]arenes
have
been
extensively
investigated
as
carrier
materials
for
applications
in
host-guest
chemistry,
nanoscience,
information
science,
and
other
domains.
Despite
its
success,
the
enantioselective
synthesis
of
pillar[n]arenes
is
challenging
has
not
yet
achieved.
Herein,
we
present
a
novel
asymmetric
extended
side-arm
strategy
synthesizing
chiral
pillar[5]arenes
through
an
iterative
copper-catalyzed
azide-alkyne
cycloaddition
reaction.
An
increase
steric
hindrance
on
both
sides
macrocyclic
molecule
efficiently
produced
wide
range
high
yields
with
excellent
enantioselectivities.
Moreover,
this
principle
enables
to
enantioselectively
functionalized
different
triazoles
using
one-pot
process.
