Angewandte Chemie,
Год журнала:
2024,
Номер
136(38)
Опубликована: Июнь 8, 2024
Abstract
Cross‐electrophile
coupling
(XEC)
between
aryl
halides
and
alkyl
is
a
streamlined
approach
for
C(sp
2
)−C(sp
3
)
bond
construction,
which
highly
valuable
in
medicinal
chemistry.
Based
on
key
Ni
II
amido
intermediate,
we
developed
selective
scalable
Ni‐catalyzed
electrochemical
XEC
reaction
(hetero)aryl
primary
secondary
halides.
Experimental
computational
mechanistic
studies
indicate
that
an
amine
ligand
slows
down
the
oxidative
addition
process
of
Ni‐polypyridine
catalyst
to
bromide
intermediate
formed
situ
during
process.
The
relatively
slow
beneficial
enhancing
selectivity
reaction.
stabilizes
–aryl
species
prevent
aryl–aryl
homo‐coupling
side
reactions
acts
as
activate
substrates.
This
electrosynthesis
system
provides
facile,
practical,
platform
formation
(hetero)aryl–alkyl
bonds
using
standard
catalysts
under
mild
conditions.
insights
from
this
work
could
serve
great
foundation
future
cross‐couplings.
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 13, 2025
ConspectusMolecular
photoelectrocatalysis,
which
combines
the
merits
of
photocatalysis
and
organic
electrosynthesis,
including
their
green
attributes
capacity
to
offer
novel
reactivity
selectivity,
represents
an
emerging
field
in
chemistry
that
addresses
growing
demands
for
environmental
sustainability
synthetic
efficiency.
This
synergistic
approach
permits
access
a
wider
range
redox
potentials,
facilitates
transformations
under
gentler
electrode
decreases
use
external
harsh
reagents.
Despite
these
potential
advantages,
this
area
did
not
receive
significant
attention
until
2019,
when
we
others
reported
first
examples
modern
molecular
photoelectrocatalysis.
These
studies
showcased
immense
hybrid
strategy,
only
inherits
strengths
its
parent
fields
but
also
unlocks
unprecedented
enabling
challenging
mild
conditions
while
minimizing
reliance
on
stoichiometric
oxidants
or
reductants.In
Account,
present
our
efforts
develop
photoelectrocatalytic
strategies
leverage
homogeneous
catalysts
facilitate
diverse
radical
reactions.
By
integrating
electrocatalysis
with
key
photoinduced
processes
such
as
single
electron
transfer
(SET),
ligand-to-metal
charge
(LMCT),
hydrogen
atom
(HAT),
have
established
methods
transform
substrates
organotrifluoroborates,
arenes,
carboxylic
acids,
alkanes
into
reactive
intermediates.
intermediates
subsequently
engage
heteroarene
C-H
functionalization
Importantly,
photoelectrochemical
catalysts,
generated
bulk
solution
readily
participate
efficient
reactions
without
undergoing
further
overoxidation
carbocations,
common
challenge
conventional
electrochemical
systems.By
integration
photoelectrocatalysis
asymmetric
catalysis,
developed
catalysis
(PEAC),
proves
be
enantioselective
synthesis
chiral
nitriles.
involves
two
relay
catalytic
cycles:
initial
process
engenders
benzylic
radicals
from
precursors
alkyl
aryl
alkenes,
C-radicals
are
then
subjected
cyanation
subsequent
copper-electrocatalytic
cycle.Within
realm
oxidative
transformations,
anode
serves
crucial
component
recycling
generating
photocatalyst,
cathode
promotes
proton
reduction.
dual
functionality
enables
via
H
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(14), С. 4024 - 4040
Опубликована: Янв. 1, 2024
This
review
provides
a
comprehensive
overview
of
metal
catalysis
in
photo-electrochemical
systems,
discussing
reaction
mechanisms
and
offering
prospects
for
this
triadic
catalytic
mode.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июнь 19, 2024
Abstract
The
simultaneous
activation
of
reactants
on
the
anode
and
cathode
via
paired
electrocatalysis
has
not
been
extensively
demonstrated.
This
report
presents
a
oxidative
reductive
catalysis
based
earth-abundant
iron/nickel
cocatalyzed
C–C
functionalization
ubiquitous
alcohols.
A
variety
alcohols
(i.e.,
primary,
secondary,
tertiary,
or
unstrained
cyclic
alcohols)
can
be
activated
at
very
low
oxidation
potential
(~0.30
V
vs.
Ag/AgCl)
photoelectrocatalysis
coupled
with
versatile
electrophiles.
reactivity
yields
wide
range
structurally
diverse
molecules
broad
functional
group
compatibility
(more
than
50
examples).
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(10), С. 2352 - 2362
Опубликована: Апрель 5, 2024
Abstract
While
the
emergence
of
electrophotochemistry
provides
opportunities,
such
a
chemistry
at
this
stage
suffers
from
limited
reaction
types
and
high
photocatalyst
loadings.
A
self‐catalyzed
electrophotosynthesis
as
well
one
with
low
loading
is
presented.
These
external‐oxidant‐free
cyclizations
are
enabling
applicable
to
range
activated
alkenes,
affording
diverse
array
thiocyanato
heterocycles
including
4‐pyrrolin‐2‐ones,
isoquinoline‐1,3‐diones,
indolo[2,1‐
]isoquinolin‐6(5
H
)‐ones,
benzoimidazo[2,1‐
)‐ones
indolin‐2‐ones,
protocols
amenable
late‐stage
diversification
complex
molecular
architectures
gram‐scale
syntheses.
Sunlight
could
serve
light
source,
be
conducted
in
an
all‐solar‐driven
mode
using
commercially
available
photovoltaic
panel
produce
electricity.
Chemical Society Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
highlights
organo-mediators
that
enable
electrochemical
reactions
via
outer-sphere
electron
transfer
(ET),
offering
advantages
such
as
availability,
tunability,
and
simplified
post-processing
compared
to
direct
electrolysis.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июнь 8, 2024
Abstract
Cross‐electrophile
coupling
(XEC)
between
aryl
halides
and
alkyl
is
a
streamlined
approach
for
C(sp
2
)−C(sp
3
)
bond
construction,
which
highly
valuable
in
medicinal
chemistry.
Based
on
key
Ni
II
amido
intermediate,
we
developed
selective
scalable
Ni‐catalyzed
electrochemical
XEC
reaction
(hetero)aryl
primary
secondary
halides.
Experimental
computational
mechanistic
studies
indicate
that
an
amine
ligand
slows
down
the
oxidative
addition
process
of
Ni‐polypyridine
catalyst
to
bromide
intermediate
formed
situ
during
process.
The
relatively
slow
beneficial
enhancing
selectivity
reaction.
stabilizes
–aryl
species
prevent
aryl–aryl
homo‐coupling
side
reactions
acts
as
activate
substrates.
This
electrosynthesis
system
provides
facile,
practical,
platform
formation
(hetero)aryl–alkyl
bonds
using
standard
catalysts
under
mild
conditions.
insights
from
this
work
could
serve
great
foundation
future
cross‐couplings.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Авг. 12, 2024
Photoelectrochemical
(PEC)
cell
is
an
ideal
platform
for
organic
transformation
because
of
its
green
benefits
and
minimal
energy
consumption.
As
emerging
methodology,
the
reaction
types
photoelectrocatalytic
synthesis
(PECOS)
are
limited
to
simple
oxidation
C–H
activation
at
current
stage.
Metal
catalysis
construction
C(sp2)–N
bonds
has
not
been
touched
yet
in
PECOS.
We
introduce
here
a
PEC
method
that
successfully
engages
Ni
mild
production
aniline
derivatives.
Experimental
computational
investigations
elucidate
addition
photoanode-generated
amine
radical
catalyst
avoids
sluggish
nucleophilic
attack,
enabling
proceed
ultra-low
potential
(–0.4
V
vs.
Ag/AgNO3)
preventing
overoxidation
products
conventional
electrochemical
synthesis.
This
synergistic
strategy
exhibits
good
functional
group
tolerance
wide
substrate
scope
on
both
aryl
halides
amines,
by
which
some
important
natural
pharmaceutical
chemicals
have
modified.
The
stage
while
metal
remains
unexplored.
Here,
authors
