Metal-centered
chirality
has
been
recognized
for
over
one
century,
and
chiral-at-metal
complexes
where
is
exclusively
attributed
to
the
metal
center
due
specific
coordination
pattern
of
achiral
ligands
around
ion,
broadly
utilized
in
diverse
areas
natural
sciences.
However,
synthesis
these
molecules
remains
constrained.
Notably,
while
asymmetric
catalysis
played
a
crucial
role
production
optically
active
organic
molecules,
its
application
less
straightforward.
In
this
study,
we
introduce
kinetic
resolution
strategy
employing
Pd-catalyzed
Suzuki-Miyaura
cross-coupling
reaction
that
efficiently
produces
chiral-at-iridium
from
racemic
mixtures
with
high
selectivity
(achieving
an
s-factor
up
133).
This
method
enables
further
relevant
chiral
metallodrugs
photosensitizers,
underscoring
practical
utility
our
approach.
Mechanistic
studies
suggest
reductive
elimination
turnover-limiting
step
cross-coupling.
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.
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.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(30), С. 16796 - 16811
Опубликована: Июль 20, 2023
Synthetic
application
of
asymmetric
catalysis
relies
on
strategic
alignment
bond
construction
to
creation
chirality
a
target
molecule.
Remote
desymmetrization
offers
distinctive
advantages
spatial
decoupling
catalytic
transformation
and
generation
stereogenic
element.
However,
such
separation
presents
substantial
difficulties
for
the
chiral
catalyst
discriminate
distant
enantiotopic
sites
through
reaction
three
or
more
bonds
away
from
prochirality
center.
Here,
we
report
strategy
that
establishes
acyclic
quaternary
carbon
stereocenters
cross-coupling
reactions
at
distal
positions
aryl
substituents.
The
new
class
amino
acid-derived
ionic
catalysts
enables
desymmetrizing
(enantiotopic-group-selective)
Suzuki-Miyaura
reaction,
Sonogashira
Buchwald-Hartwig
amination
between
diverse
diarylmethane
scaffolds
aryl,
alkynyl,
coupling
partners,
providing
rapid
access
enantioenriched
molecules
project
substituents
widely
spaced
in
three-dimensional
space.
Experimental
computational
investigations
reveal
electrostatic
steering
substrates
by
C-terminus
ligands
interactions.
Cooperative
ion-dipole
interactions
catalyst's
amide
group
potassium
cation
aid
preorganization
transmits
asymmetry
product.
This
study
demonstrates
it
is
practical
achieve
precise
long-range
stereocontrol
engineering
arrangements
catalysts'
substrate-recognizing
groups
metal
centers.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 30, 2025
Metal-centered
chirality
has
been
recognized
for
over
one
century,
and
stereogenic-at-metal
complexes
where
is
exclusively
attributed
to
the
metal
center
due
specific
coordination
pattern
of
achiral
ligands
around
ion,
broadly
utilized
in
diverse
areas
natural
science.
However,
synthesis
these
molecules
remains
constrained.
Notably,
while
asymmetric
catalysis
played
a
crucial
role
production
optically
active
organic
molecules,
its
application
less
straightforward.
In
this
study,
we
introduce
kinetic
resolution
strategy
employing
Pd-catalyzed
Suzuki-Miyaura
cross-coupling
reaction
that
efficiently
produces
stereogenic-at-iridium
from
racemic
mixtures
with
high
selectivity
(achieving
an
s-factor
up
133).
This
method
enables
further
relevant
chiral
metallodrugs
photosensitizers,
underscoring
practical
utility
our
approach.
Mechanistic
studies
suggest
reductive
elimination
likely
turnover-limiting
step
cross-coupling.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Март 10, 2025
Pillar[n]arenes
have
broad
applications
in
biological
medicine,
materials
science,
and
supramolecular
gels.
Notably,
enantiopure
pillar[5]arenes
are
valued
for
their
roles
enantioselective
host–guest
recognition,
chiral
sensing,
asymmetric
catalysis,
related
fields.
Current
methods
obtaining
pillar[n]arenes
rely
heavily
on
resolution
agents
or
HPLC
resolution.
However,
the
synthesis
of
these
compounds
via
catalysis
remains
challenging.
In
this
study,
we
develop
an
extended
side-arm
Suzuki–Miyaura
cross-coupling
strategy
to
construct
inherently
with
excellent
yields
high
enantioselectivities
using
a
palladium
catalyst
Sadphos
ligand.
The
reaction
scope
extends
beyond
arylboronic
acids
encompass
2-arylvinylboronic
other
multi-OTf-substituted
substrates,
all
efficiently
producing
desired
products.
Further
exploration
synthetic
applications,
along
photophysical
chiroptical
analyses,
confirm
potential
diverse
across
multiple
disciplines.
Enantiopure
recognition
but
current
Here,
authors
pillar[5]arenes.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(47), С. 25553 - 25558
Опубликована: Ноя. 16, 2023
Arylative
phenol
dearomatization
affords
complex,
cyclohexanone-based
scaffolds
from
simple
starting
materials,
and
asymmetric
versions
allow
access
to
valuable
enantioenriched
structures.
However,
bespoke
chiral
ligands
must
typically
be
identified
for
each
new
scaffold
variation.
We
have
addressed
this
limitation
by
applying
the
concept
of
electrostatically-directed
palladium
catalysis
whereby
sulfonated
ligand
sSPhos
engages
in
electrostatic
interactions
with
a
phenolate
substrate
via
its
associated
alkali
metal
cation.
This
approach
allows
highly
spirocyclohexadienones,
process
originally
reported
Buchwald
co-workers
predominantly
racemic
manner.
In
addition,
is
proficient
at
forming
two
other
distinct
scaffolds,
which
had
previously
required
fundamentally
different
ligands,
as
well
novel
oxygen-linked
scaffold.
envisage
that
broad
generality
displayed
will
facilitate
expansion
important
reaction
type
highlight
potential
unusual
design
principle,
harnesses
attractive
interactions.
