Abstract
Photocatalysis
is
a
powerful
tool
to
assemble
diverse
chemical
scaffolds,
yet
bottleneck
on
its
further
development
the
understanding
of
multitude
possible
pathways
when
practitioners
rely
only
oversimplified
thermodynamic
and
optical
factors.
Recently,
there
growing
number
studies
in
field
that
exploit,
inter
alia
,
kinetic
parameters
organophotocatalysts
are
synthetically
more
programmable
terms
their
redox
states
opportunities
for
aggregation
with
target
substrate.
Non‐covalent
interactions
play
key
role
enables
access
new
generation
reactivities
such
as
those
open‐shell
organophotocatalysts.
In
this
review,
we
discuss
how
targeted
structural
modifications
influence
organophotocatalytic
mechanisms
together
underlying
principles.
We
also
highlight
benefits
strategies
preassembly
static
quenching
overcome
common
reactivity
issues
(e.
g.,
diffusion
rate
limits
energetic
limits).
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(14), С. 7941 - 8002
Опубликована: Янв. 1, 2021
Electrochemistry
has
recently
gained
increased
attention
as
a
versatile
strategy
for
achieving
challenging
transformations
at
the
forefront
of
synthetic
organic
chemistry.
Electrochemistry's
unique
ability
to
generate
highly
reactive
radical
and
ion
intermediates
in
controlled
fashion
under
mild
conditions
inspired
development
number
new
electrochemical
methodologies
preparation
valuable
chemical
motifs.
Particularly,
recent
developments
electrosynthesis
have
featured
an
use
redox-active
electrocatalysts
further
enhance
control
over
selective
formation
downstream
reactivity
these
intermediates.
Furthermore,
electrocatalytic
mediators
enable
proceed
manner
that
is
mechanistically
distinct
from
purely
methods,
allowing
subversion
kinetic
thermodynamic
obstacles
encountered
conventional
synthesis.
This
review
highlights
key
innovations
within
past
decade
area
electrocatalysis,
with
emphasis
on
mechanisms
catalyst
design
principles
underpinning
advancements.
A
host
oxidative
reductive
are
discussed
grouped
according
classification
transformation
nature
electrocatalyst.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(28), С. 12567 - 12583
Опубликована: Июль 11, 2022
Visible-light
photocatalysis
and
electrocatalysis
are
two
powerful
strategies
for
the
promotion
of
chemical
reactions
that
have
received
tremendous
attention
in
recent
years.
In
contrast,
processes
combine
these
modalities,
an
area
termed
electrophotocatalysis,
until
recently
remained
quite
rare.
However,
over
past
several
years
a
number
reports
this
shown
potential
combining
power
light
electrical
energy
to
realize
new
catalytic
transformations.
Electrophotocatalysis
offers
ability
perform
photoredox
without
need
large
quantities
stoichiometric
or
superstoichiometric
oxidants
reductants
by
making
use
electrochemical
as
electron
source
sink.
addition,
electrophotocatalysis
is
readily
amenable
generation
open-shell
photocatalysts,
which
tend
exceptionally
strong
redox
potentials.
way,
potent
yet
selective
been
realized
under
relatively
mild
conditions.
This
Perspective
highlights
advances
provides
some
possible
avenues
future
work
growing
area.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
61(12)
Опубликована: Сен. 3, 2021
Synthetic
photoelectrochemistry
(PEC)
is
receiving
increasing
attention
as
a
new
frontier
for
the
generation
and
handling
of
reactive
intermediates.
PEC
permits
selective
single-electron
transfer
(SET)
reactions
in
much
greener
way
broadens
redox
window
possible
transformations.
Herein,
most
recent
contributions
are
reviewed,
demonstrating
exciting
opportunities,
namely,
combination
with
other
reactivity
paradigms
(hydrogen-atom
transfer,
radical
polar
crossover,
energy
sensitization),
scalability
up
to
multigram
scale,
novel
selectivities
SET
super-oxidations/reductions
importance
precomplexation
temporally
enable
excited
ion
catalysis.
Chemical Reviews,
Год журнала:
2023,
Номер
123(19), С. 11269 - 11335
Опубликована: Сен. 26, 2023
Late-stage
functionalization
(LSF)
constitutes
a
powerful
strategy
for
the
assembly
or
diversification
of
novel
molecular
entities
with
improved
physicochemical
biological
activities.
LSF
can
thus
greatly
accelerate
development
medicinally
relevant
compounds,
crop
protecting
agents,
and
functional
materials.
Electrochemical
synthesis
has
emerged
as
an
environmentally
friendly
platform
transformation
organic
compounds.
Over
past
decade,
electrochemical
late-stage
(eLSF)
gained
major
momentum,
which
is
summarized
herein
up
to
February
2023.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(20), С. 11163 - 11167
Опубликована: Март 4, 2021
The
electrophotocatalytic
heterofunctionalization
of
arenes
is
described.
Using
2,3-dichloro-5,6-dicyanoquinone
(DDQ)
under
a
mild
electrochemical
potential
with
visible-light
irradiation,
undergo
oxidant-free
hydroxylation,
alkoxylation,
and
amination
high
chemoselectivity.
In
addition
to
batch
reactions,
an
recirculating
flow
process
demonstrated,
enabling
the
conversion
benzene
phenol
on
gram
scale.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(44), С. 20201 - 20206
Опубликована: Окт. 31, 2022
The
development
of
efficient
and
sustainable
methods
for
decarboxylative
transformations
is
great
importance
due
to
the
ease
availability
nontoxicity
carboxylic
acids.
Despite
tremendous
efforts
in
this
area,
it
remains
challenging
develop
enantioselective
direct
from
Herein
we
disclose
a
photoelectrocatalytic
method
cyanation.
photoelectrochemical
reactions
convert
acids
enantioenriched
nitriles
by
employing
cerium/copper
relay
catalysis
with
cerium
salt
catalytic
decarboxylation
chiral
copper
complex
stereoselective
C-CN
formation.
JACS Au,
Год журнала:
2022,
Номер
2(6), С. 1488 - 1503
Опубликована: Июнь 10, 2022
Photoredox
catalysis
typically
relies
on
the
use
of
single
chromophores,
whereas
strategies,
in
which
two
different
light
absorbers
are
combined,
rare.
In
photosystems
I
and
II
green
plants,
separate
chromophores
P680
P700
both
absorb
independently
one
another,
then
their
excitation
energy
is
combined
so-called
Z-scheme,
to
drive
an
overall
reaction
that
thermodynamically
very
demanding.
Here,
we
adapt
this
concept
perform
photoredox
reactions
organic
substrates
with
input
red
photons
instead
blue
or
UV
light.
Specifically,
a
CuI
bis(α-diimine)
complex
combination
situ
formed
9,10-dicyanoanthracenyl
radical
anion
presence
excess
diisopropylethylamine
catalyzes
ca.
50
dehalogenation
detosylation
reactions.
This
dual
approach
seems
useful
because
less
damaging
has
greater
penetration
depth
than
radiation.
UV-vis
transient
absorption
spectroscopy
reveals
subtle
change
solvent
from
acetonitrile
acetone
induces
changeover
mechanism,
involving
either
dominant
photoinduced
electron
transfer
triplet-triplet
pathway.
Our
study
illustrates
mechanistic
complexity
systems
operating
under
multiphotonic
conditions,
it
provides
insights
into
how
competition
between
desirable
unwanted
steps
can
become
more
controllable.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(34), С. 18753 - 18759
Опубликована: Авг. 15, 2023
The
asymmetric
difunctionalization
of
alkenes,
a
method
transforming
readily
accessible
alkenes
into
enantioenriched
chiral
structures
high
value,
has
long
been
focal
point
organic
synthesis.
Despite
tremendous
efforts
in
this
domain,
it
remains
considerable
challenge
to
devise
enantioselective
oxidative
dicarbofunctionalization
even
though
these
transformations
can
utilize
stable
and
unfunctionalized
functional
group
donors.
In
context,
we
report
herein
photoelectrocatalytic
for
the
heteroarylcyanation
aryl
which
employs
heteroarenes
through
C-H
functionalization.
photoelectrochemical
catalysis
(PEAC)
combines
photoredox
electrocatalysis
facilitate
formation
two
C-C
bonds
operating
via
hydrogen
(H2)
evolution
obviating
need
external
chemical
oxidants.