Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(8), С. 1670 - 1706
Опубликована: Фев. 29, 2024
Abstract
The
Friedel‐Crafts
reaction
stands
as
a
powerful
synthetic
tool
for
C−H
functionalization
of
aromatic
feedstocks,
which
is
conventionally
realized
through
electrophilic
alkylation
and
acylation.
burgeoning
interests
in
axially
chiral
compounds
across
diverse
fields
have
spurred
extensive
exploration
this
classic
transformation
catalytic
atroposelective
synthesis.
Consequently,
the
past
decade
has
witnessed
rapid
expansion
various
non‐canonical
reactions,
including
arylation,
alkenylation,
halogenation,
sulfenylation,
amination
aryl
bonds,
thereby
delving
into
new
chemical
spaces.
A
range
methods
been
devised
these
significant
arene
functionalization.
This
review
provides
comprehensive
overview
cutting‐edge
synthesis
atropoisomers
categorized
three
parts
based
on
type
bond
formation
aromatics:
C(
sp
2
)−C(
3
)
formations,
formations
)−heteroatom
formations.
richness
electrophiles
modulation
atroposelectivity
by
organocatalysts,
particularly
Brønsted
acids,
are
elucidated.
We
anticipate
that
repertoire
asymmetric
will
continue
to
flourish
be
demonstrated
not
only
scientific
researches
but
also
industrial
organic
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(10)
Опубликована: Янв. 17, 2024
Abstract
An
efficient
catalytic
asymmetric
electrophilic
sulfenylation
reaction
for
the
synthesis
of
planar‐chiral
sulfur‐containing
cyclophanes
has
been
developed
first
time.
This
was
achieved
by
using
a
new
Lewis
base
catalyst
and
ortho
‐trifluoromethyl‐substituted
sulfenylating
reagent.
Using
substrates
with
low
rotational
energy
barrier,
transformation
proceeded
through
dynamic
kinetic
resolution,
high
barrier
allowed
to
undergo
resolution
process.
Meanwhile,
this
compatible
desymmetrization
process
when
symmetric
were
used.
Various
readily
obtained
in
moderate
excellent
yields
enantioselectivities
(up
97
%
yield
95
ee).
approach
used
synthesize
pharmaceutically
relevant
molecules.
Density
functional
theory
calculations
showed
that
π‐π
interactions
between
sulfenyl
group
aromatic
ring
substrate
play
crucial
role
enantioinduction
reaction.
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.
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 1147 - 1157
Опубликована: Янв. 3, 2025
This
study
describes
a
photoredox/cobalt
dual-catalyzed
asymmetric
Grignard-type
addition
reaction,
enabling
the
synthesis
of
axially
chiral
hexatomic
(six–six)
N-heterobiaryls
bearing
extra
secondary
alcohol
unit
via
an
efficient
dynamic
kinetic
transformation
racemic
N-heterobiaryl
triflate
substrates.
The
conversion
facilitated
both
photoredox
and
classical
reductive
reaction
conditions
exhibits
good
functional
group
tolerance,
broad
substrate
scope,
satisfactory
stereoselectivity.
Furthermore,
control
experiments
density
theory
calculations
provide
preliminary
mechanistic
insights.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 14, 2025
A
diverse
range
of
Pd(II)-catalyzed
enantioselective
C-H
activation
reactions
have
been
developed
to
construct
point,
axial,
and
planar
chirality.
Despite
the
importance
chiral
biaryl
scaffolds
in
bioactive
molecules
ligands,
atroposelective
functionalization
at
meta-position
remains
a
significant
challenge.
Here,
we
realized
rare
remote
meta-C-H
with
monoprotected
amino
acid
(MPAA)
ligand
racemic
transient
norbornene
mediator.
The
reaction
starts
ortho-C-H
via
kinetic
resolution
give
biaryl-palladium
intermediate,
which
subsequently
undergoes
Catellani
relay
afford
meta-functionalized
products
(S-factors
up
458).
obtained
enantioenriched
quinoline-based
atropisomers
are
ubiquitous
natural
products,
pharmaceuticals,
functional
materials.
Moreover,
unprecedented
meta-alkenylation
alkynylation
also
using
this
approach.
wide
synthetic
applications
8-aryl
quinolines,
including
synthesis
novel
P,N-ligand
materials
CPL
activity,
demonstrated.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(22)
Опубликована: Март 26, 2024
Abstract
Upgrading
CO
2
to
value‐added
chiral
molecules
via
catalytic
asymmetric
C−C
bond
formation
is
a
highly
important
yet
challenging
task.
Although
great
progress
on
the
of
centrally
carboxylic
acids
has
been
achieved,
construction
axially
with
never
reported
date.
Herein,
we
report
first
synthesis
,
which
enabled
by
nickel‐catalyzed
dynamic
kinetic
reductive
carboxylation
racemic
aza‐biaryl
triflates.
A
variety
acids,
are
valuable
but
difficult
obtain
catalysis,
generated
in
an
enantioconvergent
version.
This
new
methodology
features
good
functional
group
tolerance,
easy
scale‐up,
facile
transformation
and
avoids
cumbersome
steps,
handling
organometallic
reagents
using
stoichiometric
materials.
Mechanistic
investigations
indicate
process
induced
nickel
catalysis.
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.
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.
