Advanced Functional Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 15, 2024
Abstract
Extensive
research
over
recent
decades
has
demonstrated
the
feasibility
of
producing
stable
radical
polymers
(SRPs)
by
exploring
structure–stability
relationships.
Owing
to
their
excellent
redox
activities
and
inherent
paramagnetic
characteristics,
SRPs
are
emerging
as
key
functional
materials
with
considerable
potentials
for
various
applications
such
in
organic
electrodes,
semiconductors,
magnetic
materials,
quantum
information
technologies.
Accordingly,
this
review
provides
a
comprehensive
summary
most
widely
investigated
representative
families
SRPs.
Innovative
strategies
design
synthesis
relationship
among
physicochemical
properties,
electronic
structures,
resulting
functionalities
these
discussed.
Moreover,
advancements
highlighted.
Finally,
challenges
chemistry
material
functionalization,
offering
insights
into
transformative
potential
future
applications,
emphasized.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(20)
Published: March 13, 2024
Abstract
Since
Friedrich
Wöhler's
groundbreaking
synthesis
of
urea
in
1828,
organic
over
the
past
two
centuries
has
predominantly
relied
on
exploration
and
utilization
chemical
reactions
rooted
two‐electron
heterolytic
ionic
chemistry.
While
one‐electron
homolytic
radical
chemistry
is
both
rich
fundamental
reactivities
attractive
with
practical
advantages,
synthetic
application
been
long
hampered
by
formidable
challenges
associated
control
reactivity
selectivity
high‐energy
intermediates.
To
fully
harness
untapped
potential
for
synthesis,
there
a
pressing
need
to
formulate
radically
different
concepts
broadly
applicable
strategies
address
these
outstanding
issues.
In
pursuit
this
objective,
researchers
have
actively
developing
metalloradical
catalysis
(MRC)
as
comprehensive
framework
guide
design
general
approaches
controlling
stereoselectivity
reactions.
Essentially,
MRC
exploits
metal‐centered
radicals
present
open‐shell
metal
complexes
catalysts
activation
substrates
generate
metal‐entangled
key
intermediates
govern
reaction
pathway
stereochemical
course
subsequent
catalytic
processes.
Different
from
conventional
transition
complexes,
operates
through
utilizing
stepwise
mechanisms.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(4), P. 2351 - 2357
Published: Jan. 17, 2024
Cross-coupling
catalysts
typically
react
and
unite
functionally
distinct
partners
via
sequential
inner-sphere
elementary
steps:
coordination,
migratory
insertion,
reductive
elimination,
etc.
Here,
we
report
a
single
catalyst
that
cross-couples
styrenes
benzyl
bromides
iterative
outer-sphere
metal–ligand-carbon
interactions.
Each
partner
forms
stabilized
radical
intermediate,
yet
heterocoupled
products
predominate.
The
system
is
redox-neutral
and,
thus,
avoids
exogenous
oxidants,
resulting
in
simple
scalable
conditions.
Numerous
variations
of
alkene
hydrobenzylation
are
made
possible,
including
access
to
the
privileged
heterodibenzyl
(1,2-diarylethane)
motif
challenging
quaternary
carbon
variants.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(41)
Published: July 3, 2024
Skeletal
molecular
editing
gained
considerable
recent
momentum
and
emerged
as
a
uniquely
powerful
tool
for
late-stage
diversifications.
Thus
far,
superstoichiometric
amounts
of
costly
hypervalent
iodine(III)
reagents
were
largely
required
skeletal
indole
editing.
In
contrast,
we
herein
show
that
electricity
enables
sustainable
nitrogen
atom
insertion
reactions
to
give
bio-relevant
quinazoline
scaffolds
without
stoichiometric
chemical
redox-waste
product.
The
transition
metal-free
electro-editing
was
enabled
by
the
oxygen
reduction
reaction
(ORR)
proved
robust
on
scale,
while
tolerating
variety
valuable
functional
groups.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 22, 2025
A
catalytic
radical
process
has
been
developed
via
metalloradical
catalysis
(MRC)
for
1,6-C(sp3)-H
amination
with
concurrent
control
of
site-,
chemo-,
and
enantioselectivity.
Supported
by
an
optimal
D2-symmetric
chiral
amidoporphyrin
ligand,
the
Co(II)-based
system
effectively
catalyzes
chemoselective
propargylic,
allylic,
benzylic
C-H
bonds
at
1,6-
over
1,5-positions
alkoxysulfonyl
azides,
achieving
high
This
Co(II)-catalyzed
process,
which
operates
room
temperature,
is
applicable
to
a
broad
range
azides
tolerance
functional
groups,
enabling
efficient
construction
six-membered
sulfamidates
in
yields
excellent
enantioselectivities.
Comprehensive
experimental
investigations,
complemented
computational
studies,
elucidate
stepwise
mechanism
underlying
this
transformation.
The
resulting
cyclic
from
enantioselective
can
undergo
stereospecific
ring-opening
reactions
various
nucleophiles,
affording
γ-functionalized
α-chiral
amines
while
retaining
original
enantiopurity.
Since
are
readily
synthesized
widely
available
alcohols
through
nucleophilic
azide
transfer,
union
ionic
processes
constitutes
versatile
1,3-difunctionalization
alcohols.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 21, 2025
Transition-metal
hydrides
stand
as
indispensable
intermediates
in
both
energy
conversion
and
organic
synthesis.
Their
electrochemical
generation
represents
a
compelling
sustainable
approach,
enabling
precise
control
over
the
reactivity
expanding
scope
of
electrocatalytic
hydrogenation
isomerization.
However,
major
challenge
Ni-catalyzed
is
competing
hydrogen
evolution
reaction
(HER),
which
has
led
to
various
innovative
strategies
aimed
at
circumventing
Ni-H
formation.
Here,
we
pursued
an
alternative
approach
by
designing
bifunctional
ligand
with
pendant
amine
moiety
promote
This
design
enabled
selective
(semi)hydrogenation
diverse
range
substrates,
including
terminal
internal
alkynes,
alkenes,
aldehydes,
achieving
unprecedented
substrate
scope.
Remarkably,
also
demonstrated
tunable
positional
selectivity
for
olefin
isomerization
employing
different
types
proton
sources.
Our
method
exhibits
excellent
functional
group
tolerance,
streamlining
access
pharmaceuticals
their
derivatives.
Computational
studies
revealed
crucial,
noninnocent
role
source
modulating
metal
hydride
selectivity,
either
through
bonding,
direct
protonation
amine,
or
facilitation
protodemetalation.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(20)
Published: March 13, 2024
Abstract
Since
Friedrich
Wöhler's
groundbreaking
synthesis
of
urea
in
1828,
organic
over
the
past
two
centuries
has
predominantly
relied
on
exploration
and
utilization
chemical
reactions
rooted
two‐electron
heterolytic
ionic
chemistry.
While
one‐electron
homolytic
radical
chemistry
is
both
rich
fundamental
reactivities
attractive
with
practical
advantages,
synthetic
application
been
long
hampered
by
formidable
challenges
associated
control
reactivity
selectivity
high‐energy
intermediates.
To
fully
harness
untapped
potential
for
synthesis,
there
a
pressing
need
to
formulate
radically
different
concepts
broadly
applicable
strategies
address
these
outstanding
issues.
In
pursuit
this
objective,
researchers
have
actively
developing
metalloradical
catalysis
(MRC)
as
comprehensive
framework
guide
design
general
approaches
controlling
stereoselectivity
reactions.
Essentially,
MRC
exploits
metal‐centered
radicals
present
open‐shell
metal
complexes
catalysts
activation
substrates
generate
metal‐entangled
key
intermediates
govern
reaction
pathway
stereochemical
course
subsequent
catalytic
processes.
Different
from
conventional
transition
complexes,
operates
through
utilizing
stepwise
mechanisms.
