Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(25)
Published: April 26, 2023
Atroposelective
cross-coupling
is
one
of
the
most
appealing
routes
to
construct
axially
chiral
binaphthyl
molecules
due
modular
and
succinct
nature.
Although
transition-metal-catalyzed
cross-couplings
offer
reliable
synthetic
means,
alternative
reaction
modes
that
could
be
applied
broader
substrate
range
without
their
pre-functionalization
highly
desirable.
Herein
we
show
application
Brønsted
acid
catalyst
as
organocatalyst
accomplish
1-azonaphthalenes
2-naphthols
with
high
efficiency,
exclusive
C4-selectivity
well
excellent
enantioselectivity
functional
group
compatibility.
The
identification
acylimidazolinone
auxiliary
for
azo
activating
group,
effective
remote
control
arene
resonance
effect
synergistically
play
key
roles
in
development
this
method.
utility
further
demonstrated
by
transformations
products
into
other
compounds
perfectly
retained
axial
chirality.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(12), P. 6944 - 6952
Published: March 15, 2023
Enantioselective
metallaphotoredox
catalysis,
which
combines
photoredox
catalysis
and
asymmetric
transition-metal
has
become
an
effective
approach
to
achieve
stereoconvergence
under
mild
conditions.
Although
many
impressive
synthetic
approaches
have
been
developed
access
central
chirality,
the
construction
of
axial
chirality
by
still
remains
underexplored.
Herein,
we
report
two
visible
light-induced
cobalt-catalyzed
reductive
couplings
biaryl
dialdehydes
synthesize
axially
chiral
aldehydes
(60
examples,
up
98%
yield,
>19:1
dr,
>99%
ee).
This
protocol
shows
good
functional
group
tolerance,
broad
substrate
scope,
excellent
diastereo-
enantioselectivity.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(33), P. 15026 - 15032
Published: Aug. 15, 2022
Axial
chirality
features
prominently
in
molecules
of
biological
interest
as
well
chiral
catalyst
designs,
and
atropisomeric
2,2′-biphenols
are
particularly
prevalent.
Atroposelective
metal-catalyzed
cross-coupling
is
an
attractive
modular
approach
to
access
enantioenriched
biphenols,
yet
existing
protocols
cannot
achieve
this
directly.
We
address
challenge
through
the
use
enantiopure,
sulfonated
SPhos
(sSPhos),
ligand
that
has
until
now
been
used
only
racemic
form
derives
its
from
axis
introduced
sulfonation.
believe
noncovalent
interactions
involving
sulfonate
group
responsible
for
high
levels
asymmetric
induction
we
obtain
2,2′-biphenol
products
Suzuki–Miyaura
coupling,
have
developed
a
highly
practical
resolution
sSPhos
via
diastereomeric
salt
recrystallization.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(9), P. 6283 - 6293
Published: Feb. 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.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(8)
Published: Jan. 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.
