Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(4), P. 917 - 921
Published: Jan. 18, 2024
A
chiral
carbene-catalyzed
chemo-
and
enantioselective
reaction
with
racemic
biaryl
aldehydes
α-bromoenals
is
developed
for
access
to
axially
2-arylbenzaldehydes
through
atroposelective
dynamic
kinetic
resolution
(DKR)
processes.
This
DKR
strategy
can
tolerate
a
broad
scope
of
substrates
diverse
functionalities.
The
2-aryl
benzaldehyde
products
generally
afford
moderate
good
yields
enantioselectivities.
molecules
afforded
from
the
current
approach
are
variable
simple
transformations
functional
excellent
optical
purities.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(17), P. 10641 - 10727
Published: Aug. 28, 2023
Enantiomers,
where
chirality
arises
from
restricted
rotation
around
a
single
bond,
are
atropisomers.
Due
to
the
unique
nature
of
origins
their
chirality,
synthetic
strategies
access
these
compounds
in
an
enantioselective
manner
differ
those
used
prepare
enantioenriched
containing
point
arising
unsymmetrically
substituted
carbon
center.
In
particular
stereodynamic
transformations,
such
as
dynamic
kinetic
resolutions,
thermodynamic
and
deracemizations,
which
rely
on
ability
racemize
or
interconvert
enantiomers,
promising
set
transformations
optically
pure
late
stage
sequence.
Translation
approaches
with
atropisomers
requires
expanded
toolbox
for
epimerization/racemization
provides
opportunity
develop
new
conceptual
framework
synthesis
compounds.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(4), P. 2565 - 2575
Published: Feb. 6, 2023
We
present
herein
an
unprecedented
stereoselective
synthesis
of
triaryl-2-pyrones
with
monoaxial
or
contiguous
diaxes
from
readily
available
starting
materials.
This
N-heterocyclic
carbene
catalysis
method
adopts
atroposelective
annulation
2-aryketones
ynals
under
oxidative
conditions.
The
includes
the
construction
one
two
axes
in
a
single
operation,
achieves
step
economy,
and
affords
axially
chiral
moderate
to
good
yields,
high
excellent
enantioselectivities.
DFT
calculations
relative
energies
stereoisomers
rotational
barriers
were
performed.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Jan. 15, 2024
Abstract
The
construction
of
N–N
axially
chiral
motifs
is
an
important
research
topic,
owing
to
their
wide
occurrence
in
natural
products,
pharmaceuticals
and
ligands.
One
efficient
method
the
atroposelective
dihydropyrimidin-4-one
formation.
We
present
herein
a
direct
catalytic
synthesis
atropisomers
with
simultaneous
creation
contiguous
axial
central
chirality
by
oxidative
NHC
(
N
-heterocyclic
carbenes)
catalyzed
(3
+
3)
cycloaddition.
Using
our
method,
we
are
able
synthesize
structurally
diverse
pyrroles
indoles
vicinal
or
bearing
2,3-dihydropyrimidin-4-one
moiety
moderate
good
yields
excellent
enantioselectivities.
Further
synthetic
transformations
obtained
derivative
products
demonstrated.
reaction
mechanism
origin
enantioselectivity
understood
through
DFT
calculations.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(14)
Published: Jan. 31, 2022
Axially
chiral
aldehydes
have
received
increasing
attention
in
enantioselective
catalysis.
However,
only
very
few
catalytic
methods
been
developed
to
construct
structurally
diverse
axially
aldehydes.
We
herein
describe
an
NHC-catalyzed
atroposelective
esterification
of
biaryl
dialdehydes
as
a
general
and
practical
strategy
for
the
construction
Mechanistic
studies
indicate
that
coupling
proceeds
through
novel
combination
desymmetrization
kinetic
resolution.
This
protocol
features
excellent
enantioselectivity,
mild
conditions,
good
functional-group
tolerance,
applicability
late-stage
functionalization
provides
modular
platform
synthesis
their
derivatives.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(12), P. 4564 - 4570
Published: Jan. 1, 2024
We
present
NHC-catalyzed
atroposelective
esterification
of
prochiral
dialdehydes,
delivering
enantioenriched
axially
chiral
diaryl
ethers.
Matched
kinetic
resolutions
amplify
the
enantioselectivity
by
removing
minor
enantiomers
via
over-functionalization.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(6), P. 1269 - 1284
Published: Jan. 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.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(9), P. 6926 - 6935
Published: April 18, 2024
The
synthesis
of
N–N
axial
compounds
containing
aromatic
acyl
amides
using
common
acylation
reagents
remains
challenging.
We
describe
a
highly
atropenantioselective
N-aminoindoles
axes.
A
chiral
cyclic
isothiourea
is
used
as
the
sole
organic
catalyst
in
transformation
N-acylation
reaction.
Aroyl
chlorides
have
been
to
construct
atropisomeric
through
N-acylation.
N-aminoindole
products,
which
bear
stereogenic
axes,
were
synthesized
with
high
yields
and
enantioselectivities.
Some
enantiopure
products
exhibited
promising
antibacterial
activities
against
plant
pathogens.
