Angewandte Chemie,
Год журнала:
2023,
Номер
135(31)
Опубликована: Июнь 2, 2023
Abstract
Chiral
amines
are
broadly
used
compounds
in
pharmaceutical
industry
and
organic
synthesis,
reductive
amination
reactions
have
been
the
most
appreciated
methods
for
their
syntheses.
However,
one‐step
transfer
hydrogenative
direct
asymmetric
(THDARA)
that
could
expand
scope,
simplify
operation
eliminate
use
of
additives
has
challenging.
In
this
work,
based
on
Xiao's
racemic
2010
our
recent
work
novel
chiral
pyridine
ligands,
half‐sandwich
iridium
catalysts
were
rationally
designed
synthesized.
Using
optimized
catalyst
azeotropic
mixture
formic
acid
triethylamine
as
hydrogen
source,
a
broad
range
α‐chiral
(hetero)aryl
amines,
including
various
polar
functional
groups
heterocycles,
prepared
generally
high
yield
enantioselectivity
under
mild
operationally
simple
conditions.
Density
theory
(DFT)
calculation
catalytically
active
Ir−H
species
key
hydride
step
supported
pyridine‐induced
stereospecific
generation
center,
enantioselection
by
taming
highly
flexible
transition
structure
with
multiple
attractive
non‐covalent
interactions.
This
introduced
type
effective
simplified
approach
to
medicinally
important
well
rare
example
robust
enantioselective
transition‐metal
catalysis.
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 19, 2025
ConspectusIn
recent
years,
our
research
group
has
dedicated
significant
effort
to
the
field
of
asymmetric
organometallic
electrochemical
synthesis
(AOES),
which
integrates
electrochemistry
with
transition
metal
catalysis.
On
one
hand,
we
have
rationalized
that
compounds
can
serve
as
molecular
electrocatalysts
(mediators)
reduce
overpotentials
and
enhance
both
reactivity
selectivity
reactions.
other
conditions
for
catalysis
be
substantially
improved
through
electrochemistry,
enabling
precise
modulation
metal's
oxidation
state
by
controlling
potentials
regulating
electron
transfer
rate
via
current
adjustments.
This
synergistic
approach
addresses
key
challenges
inherent
in
traditional
catalysis,
particularly
those
related
use
redox-active
chemical
reagents.
Furthermore,
redox
conveniently
tuned
modifying
their
ligands,
thereby
governing
reaction
regioselectivity
stereoselectivity.
As
a
result,
AOES
emerged
powerful
promising
tool
chiral
compounds.In
this
Account,
summarize
contextualize
efforts
AOES.
Our
primary
strategy
involves
leveraging
controllability
potential
regulate
organometallics,
facilitating
desired
An
efficient
platform
was
established
under
mild
conditions,
significantly
reducing
reliance
on
been
systematically
categorized
into
three
sections
based
distinct
electrolysis
modes:
combined
anodic
oxidation,
cathodic
reduction,
paired
electrolysis.
In
each
section,
highlight
innovative
discoveries
tailored
unique
characteristics
respective
modes.In
many
transformations,
metal-catalyzed
reactions
involving
reagents
utilizing
exhibit
similar
reactivities.
However,
also
observed
notable
differences
certain
cases.
These
findings
include
following:
(1)
Enhanced
efficiency
synthesis:
instance,
Rh-catalyzed
enantioselective
functionalization
C–H
bonds
demonstrates
superior
efficiency.
(2)
Expanded
scope
transformations:
previously
challenging
achieved
due
tunability
potentials.
A
example
is
reductive
coupling
aryl
chlorides,
expands
range
accessible
transformations.
Additionally,
mechanistic
studies
explore
techniques
intrinsic
such
controlled
experiments,
impact
electrode
materials
catalyst
performance,
cyclic
voltammetry
studies.
investigations
provide
more
intuitive
understanding
behavior
catalysts
study
mechanisms,
guide
design
new
catalytic
systems.The
advancements
offer
robust
environmentally
friendly
sustainable
selective
By
integrating
developed
versatile
organic
not
only
enhances
but
reduces
environmental
impact.
We
anticipate
Account
will
stimulate
further
innovation
realm
AOES,
leading
discovery
systems
development
synthetic
methodologies.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Авг. 19, 2023
The
precise
and
efficient
construction
of
axially
chiral
scaffolds,
particularly
toward
the
aryl-alkene
atropoisomers
with
impeccably
full
enantiocontrol
highly
structural
diversity,
remains
greatly
challenging.
Herein,
we
disclose
an
organocatalytic
asymmetric
nucleophilic
aromatic
substitution
(SNAr)
reaction
aldehyde-substituted
styrenes
involving
a
dynamic
kinetic
resolution
process
via
hemiacetal
intermediate,
offering
novel
facile
way
to
significant
axial
styrene
scaffolds.
Upon
treatment
aldehyde-containing
bearing
(o-hydroxyl)aryl
unit
commonly
available
fluoroarenes
in
presence
peptide-phosphonium
salts,
SNAr
exquisite
bridged
biaryl
lactol
intermediate
undergoes
smoothly
furnish
series
decorated
various
functionalities
bioactive
fragments
high
stereoselectivities
(up
>99%
ee)
complete
E/Z
selectivities.
These
resulting
motifs
are
important
building
blocks
for
preparation
diverse
functionalized
styrenes,
which
have
great
potential
as
privileged
ligands/catalysts
synthesis.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(6), С. 957 - 970
Опубликована: Март 6, 2024
ConspectusThe
innovation
of
chiral
ligands
has
been
crucial
for
the
asymmetric
synthesis
functional
molecules,
as
demonstrated
by
several
types
widely
applied
"privileged"
ligands.
In
this
context,
pyridine-derived
ligands,
far
some
oldest
and
most
utilized
in
catalysis,
have
attracted
considerable
research
interest
past
half-century.
However,
development
broadly
applicable
pyridine
units
(CPUs)
plagued
intertwining
challenges,
thus
delaying
advancements
many
reactions.This
Account
aims
to
summarize
recent
progress
new
CPU-containing
focusing
on
a
rationally
designed,
modular,
tunable
CPU
developed
our
laboratory.
A
significant
problem
thwarting
conventional
designs
is
paradox
between
broad
reactivity
stereoselectivity;
that
is,
while
enhanced
stereoselectivity
may
be
achieved
introducing
elements
close
N
atom,
concomitant
increase
local
steric
hindrance
often
limits
catalytic
activity
scope.
Our
newly
features
rigid
[6-5-3]
fused-ring
framework
spirocyclic
ketal
side
wall.
The
well-defined
three-dimensional
structure
minimizes
(inner
layer)
tunes
peripheral
environment
(outer
remote
substituents,
securing
stereoselectivity.
Different
chelating
were
readily
assembled
using
structural
module,
with
applications
mechanistically
diverse
transition-metal-catalyzed
reactions.
Thus,
series
2,2′-bipyridine
successfully
employed
general,
efficient,
highly
enantioselective
nickel-catalyzed
intermolecular
reductive
addition,
Ullmann
coupling
ortho-chlorinated
aryl
aldehydes,
carboxylation
benzylic
(pseudo)halides
CO2.
Notably,
these
exhibited
superior
reactions
compared
common
N-based
iridium-catalyzed
C–H
borylation
was
N,B-bidentate
ligand.
Furthermore,
challenging,
additive-free,
broad-scope
transfer
hydrogenative
direct
amination
half-sandwich
iridium
catalyst
supported
N,C-bidentate
excellent
performance
high
stereoselectivity,
which,
when
combined
experimental
computational
mechanistic
investigations,
"double-layer
control"
design
concept.Considering
described
herein
should
inspire
creation
novel
catalysts
drive
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(51)
Опубликована: Окт. 27, 2022
In
contrast
to
previous
approaches
chiral
α-aryl
carboxylic
acids
that
based
on
reactions
using
hazardous
gases,
pressurized
setup
and
mostly
noble
metal
catalysts,
in
this
work,
a
nickel-catalyzed
general,
efficient
highly
enantioselective
carboxylation
reaction
of
racemic
benzylic
(pseudo)halides
under
mild
conditions
atmospheric
CO2
has
been
developed.
A
unique
2,2'-bipyridine
ligand
named
Me-SBpy
featuring
compact
polycyclic
skeleton
enabled
both
high
reactivity
stereoselectivity.
The
utility
method
demonstrated
by
synthesis
various
(30
examples,
up
95
%
yield
99
:
1
er),
including
profen
family
anti-inflammatory
drugs
transformations
the
as
key
intermediates.
Based
mechanistic
experimental
results,
plausible
catalytic
cycle
involving
Ni-complex/radical
equilibrium
Lewis
acid-assisted
activation
proposed.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Авг. 23, 2024
Atropisomeric
biaryls
bearing
carbonyl
groups
have
attracted
increasing
attention
due
to
their
prevalence
in
diverse
bioactive
molecules
and
crucial
role
as
efficient
organo-catalysts
or
ligands
asymmetric
transformations.
However,
preparation
often
involves
tedious
multiple
steps,
the
direct
synthesis
via
carbonylation
has
scarcely
been
investigated.
Herein,
we
report
an
palladium-catalyzed
enantioconvergent
aminocarbonylation
of
racemic
heterobiaryl
triflates
with
amines
dynamic
kinetic
transformation
(DyKAT).
This
protocol
features
a
broad
substrate
scope
excellent
compatibility
for
rapid
construction
axially
chiral
amides
good
high
yields
enantioselectivities.
Detailed
mechanistic
investigations
discover
that
base
can
impede
intramolecular
hydrogen
bond-assisted
axis
rotation
products,
thus
allowing
success
achieve
enantioselectivity.
Moreover,
achieved
be
directly
utilized
N,N,N-pincer
copper-catalyzed
enantioselective
formation
C(sp3)-N
C(sp3)-P
bonds.
Axially
containing
not
only
exist
various
drug
candidates
but
also
serve
authors
transformation.
ACS Catalysis,
Год журнала:
2025,
Номер
15(3), С. 1522 - 1531
Опубликована: Янв. 11, 2025
Axially
chiral
biaryl
benzylamines
are
present
in
numerous
natural
products,
pharmaceuticals,
ligands,
and
catalysts.
However,
the
direct
catalytic
synthesis
of
these
functional
molecules
using
a
robust
strategy
remains
formidable
challenge.
Reductive
amination
desymmetrization
dialdehydes
offers
powerful
approach
for
construction
axially
but
suffers
from
extensive
undesirable
side
reactions.
Herein,
we
engineered
ancestral
imine
reductases
to
enable
reductive
dialdehydes,
allowing
wide
range
with
up
99%
conversion
enantiomeric
excess
(ee).
The
ratio
product
byproducts
was
97:3
over
90:10
most
cases.
This
work
presents
an
alternative
accessing
will
stimulate
development
associated
bioactive
catalysts/ligands.