Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(44)
Опубликована: Авг. 16, 2023
Abstract
Electron‐deficient
acridones
and
in
situ
generated
acridinium
salts
are
reported
as
potent,
closed‐shell
photooxidants
that
undergo
surprising
mechanisms.
When
bridging
acyclic
triarylamine
catalysts
with
a
carbonyl
group
(acridones),
this
completely
diverts
their
behavior
away
from
open‐shell,
radical
cationic,
‘beyond
diffusion’
photocatalysis
to
closed‐shell,
neutral,
diffusion‐controlled
photocatalysis.
Brønsted
acid
activation
of
dramatically
increases
excited
state
oxidation
power
(by
+0.8
V).
Upon
reduction
protonated
acridones,
they
transform
electron‐deficient
even
more
potent
(*
E
1/2
=+2.56–3.05
V
vs
SCE).
These
oxidize
arenes
where
conventional
salt
have
thusfar
been
limited
electron‐rich
arenes.
Surprisingly,
upon
photoexcitation
these
appear
two
electron
reductive
quenching
form
acridinide
anions,
spectroscopically‐detected
forms.
This
new
behaviour
is
partly
enabled
by
catalyst
preassembly
the
arene,
contrasts
SET
salts.
Critically,
study
illustrates
how
redox
active
chromophoric
molecules
initially
considered
photocatalysts
can
during
reaction
catalytically
species
different
spectroscopic
properties.
Chemical Communications,
Год журнала:
2023,
Номер
59(24), С. 3487 - 3506
Опубликована: Янв. 1, 2023
This
review
mainly
summarizes
some
important
works
and
recent
advancements
in
the
electrophotocatalytic
strategy
since
its
development
(2019–2022)
introduces
catalytic
mechanism
of
electro–photocatalysts
detail.
Advanced Materials,
Год журнала:
2024,
Номер
36(21)
Опубликована: Фев. 11, 2024
Abstract
Photoelectrochemical
(PEC)
catalysis
provides
the
most
promising
avenue
for
producing
value‐added
chemicals
and
consumables
from
renewable
precursors.
Over
last
decades,
PEC
catalysis,
including
reduction
of
feedstock,
oxidation
organics,
activation
functionalization
C─C
C─H
bonds,
are
extensively
investigated,
opening
new
opportunities
employing
technology
in
upgrading
readily
available
resources.
However,
several
challenges
still
remain
unsolved,
hindering
commercialization
process.
This
review
offers
an
overview
targeted
at
synthesis
high‐value
sustainable
First,
fundamentals
evaluating
reactions
context
product
both
anode
cathode
recalled.
Then,
common
photoelectrode
fabrication
methods
that
have
been
employed
to
produce
thin‐film
photoelectrodes
highlighted.
Next,
advancements
systematically
reviewed
discussed
conversion
various
feedstocks
highly
valued
chemicals.
Finally,
prospects
field
presented.
aims
facilitating
further
development
precursors
products
other
pharmaceuticals.
Chemical Communications,
Год журнала:
2021,
Номер
57(36), С. 4424 - 4427
Опубликована: Янв. 1, 2021
The
merging
of
decatungstate
photocatalysis
with
electrochemistry
enabled
the
net-oxidative
alkylation
benzothiazoles
aliphatic
hydrogen
donors
featuring
strong
C(sp3)–H
bonds.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(19), С. 7247 - 7252
Опубликована: Май 5, 2021
A
method
for
the
acetoxyhydroxylation
of
olefins
with
syn
stereoselectivity
under
electrophotocatalytic
conditions
is
described.
The
procedure
uses
a
trisaminocyclopropenium
(TAC)
ion
catalyst
visible
light
irradiation
controlled
electrochemical
potential
to
convert
aryl
corresponding
glycol
monoesters
high
chemo-
and
diastereoselectivity.
This
reaction
can
be
performed
in
batch
or
flow,
enabling
multigram
synthesis
monoester
products.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(39), С. 21418 - 21425
Опубликована: Июль 20, 2021
Herein,
we
disclose
that
electrochemical
stimulation
induces
new
photocatalytic
activity
from
a
range
of
structurally
diverse
conventional
photocatalysts.
These
studies
uncover
electron-primed
photoredox
catalyst
capable
promoting
the
reductive
cleavage
strong
C(sp2
)-N
and
)-O
bonds.
We
illustrate
several
examples
synthetic
utility
these
deeply
reducing
but
otherwise
safe
mild
catalytic
conditions.
Finally,
employ
current
measurements
to
perform
reaction
progress
kinetic
analysis.
This
technique
reveals
improved
this
system
is
consequence
an
enhanced
stability
profile.
The
Minisci
alkylation
of
N-heteroarenes
with
unactivated
alkanes
under
external
oxidant-free
conditions
provides
an
economically
attractive
route
to
access
alkylated
but
remains
underdeveloped.
Herein,
a
new
electrophotocatalytic
strategy
alkyl
radicals
from
strong
C(sp3
)-H
bonds
was
reported
for
the
following
reactions
in
absence
chemical
oxidants.
This
realized
first
example
cerium-catalyzed
reaction
directly
abundant
excellent
atom
economy.
It
is
anticipated
that
general
design
principle
would
enrich
catalytic
strategies
explore
functionalizations
H2
evolution.
ACS Catalysis,
Год журнала:
2022,
Номер
12(17), С. 10661 - 10667
Опубликована: Авг. 16, 2022
We
report
an
electrophotochemical
metal-catalyzed
strategy
that
harnesses
the
power
of
light
and
electricity
for
radical
decarboxylative
functionalization
aliphatic
carboxylic
acids.
This
environmentally
friendly
protocol
smoothly
converts
a
diverse
array
acids
into
corresponding
alkyl
azides
without
using
chemical
oxidants
or
azido-group
transfer
reagents.
The
visible
energy
electric
can
be
applied
in
spatially
separated
fashion
with
modular
electro-flow-cell
large-scale
synthesis.
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Июль 8, 2022
The
direct
hydroxylation
of
arene
C-H
bonds
is
a
highly
sought-after
transformation
but
remains
an
unsolved
challenge
due
to
the
difficulty
in
efficient
and
regioselective
oxygenation
high
reactivity
phenolic
products
leading
overoxidation.
Herein
we
report
electrochemical
arenes
continuous
flow
for
synthesis
phenols.
method
characterized
by
broad
scope
(compatible
with
diverse
electronic
properties),
mild
conditions
without
any
catalysts
or
chemical
oxidants,
excellent
scalability
as
demonstrated
production
1
mol
(204
grams)
one
phenol
products.
Chemical Society Reviews,
Год журнала:
2023,
Номер
53(1), С. 263 - 316
Опубликована: Дек. 7, 2023
The
employment
of
light
and/or
electricity
-
alternatively
to
conventional
thermal
energy
unlocks
new
reactivity
paradigms
as
tools
for
chemical
substrate
activations.
This
leads
the
development
synthetic
reactions
and
a
vast
expansion
spaces.
review
summarizes
recent
developments
in
photo-
electrochemical
activation
strategies
functionalization
strong
bonds
particularly
carbon-heteroatom
(C-X)
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Окт. 16, 2023
Organoboron
compounds
are
of
high
significance
in
organic
synthesis
due
to
the
unique
versatility
boryl
substituents
access
further
modifications.
The
demand
for
incorporation
moieties
into
molecular
structures
has
witnessed
significant
progress,
particularly
C(sp3)-H
borylation
hydrocarbons.
Taking
advantage
special
characteristics
photo/electrochemistry,
we
herein
describe
development
an
oxidative
reaction
under
metal-
and
oxidant-free
conditions,
enabled
by
photoelectrochemical
strategy.
exhibits
broad
substrate
scope
(>57
examples),
includes
use
simple
alkanes,
halides,
silanes,
ketones,
esters
nitriles
as
viable
substrates.
Notably,
unconventional
regioselectivity
is
achieved,
with
coupling
site
selectively
located
distal
methyl
group.
Our
method
operationally
easily
scalable,
offers
a
feasible
approach
one-step
high-value
organoboron
building
blocks
from
hydrocarbons,
which
would
provide
ample
opportunities
drug
discovery.
