Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 12, 2024
Since
the
seminal
report
by
Adachi
and
co-workers
in
2012,
there
has
been
a
veritable
explosion
of
interest
design
thermally
activated
delayed
fluorescence
(TADF)
compounds,
particularly
as
emitters
for
organic
light-emitting
diodes
(OLEDs).
With
rapid
advancements
innovation
materials
design,
efficiencies
TADF
OLEDs
each
primary
color
points
well
white
devices
now
rival
those
state-of-the-art
phosphorescent
emitters.
Beyond
electroluminescent
devices,
compounds
have
also
found
increasing
utility
applications
numerous
related
fields,
from
photocatalysis,
to
sensing,
imaging
beyond.
Following
our
previous
review
2017
(
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 1925 - 2016
Published: Sept. 29, 2021
The
fields
of
C–H
functionalization
and
photoredox
catalysis
have
garnered
enormous
interest
utility
in
the
past
several
decades.
Many
different
scientific
disciplines
relied
on
strategies
including
natural
product
synthesis,
drug
discovery,
radiolabeling,
bioconjugation,
materials,
fine
chemical
synthesis.
In
this
Review,
we
highlight
use
reactions.
We
separate
review
into
inorganic/organometallic
catalysts
organic-based
catalytic
systems.
Further
subdivision
by
reaction
class─either
sp2
or
sp3
functionalization─lends
perspective
tactical
for
these
methods
synthetic
applications.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2017 - 2291
Published: Nov. 23, 2021
We
present
here
a
review
of
the
photochemical
and
electrochemical
applications
multi-site
proton-coupled
electron
transfer
(MS-PCET)
in
organic
synthesis.
MS-PCETs
are
redox
mechanisms
which
both
an
proton
exchanged
together,
often
concerted
elementary
step.
As
such,
MS-PCET
can
function
as
non-classical
mechanism
for
homolytic
bond
activation,
providing
opportunities
to
generate
synthetically
useful
free
radical
intermediates
directly
from
wide
variety
common
functional
groups.
introduction
practitioner’s
guide
reaction
design,
with
emphasis
on
unique
energetic
selectivity
features
that
characteristic
this
class.
then
chapters
oxidative
N–H,
O–H,
S–H,
C–H
homolysis
methods,
generation
corresponding
neutral
species.
Then,
reductive
PCET
activations
involving
carbonyl,
imine,
other
X═Y
π-systems,
heteroarenes,
where
ketyl,
α-amino,
heteroarene-derived
radicals
be
generated.
Finally,
we
asymmetric
catalysis
materials
device
applications.
Within
each
chapter,
subdivide
by
group
undergoing
homolysis,
thereafter
type
transformation
being
promoted.
Methods
published
prior
end
December
2020
presented.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(13), P. 7587 - 7680
Published: Jan. 1, 2021
Organic
compounds
that
show
Thermally
Activated
Delayed
Fluorescence
(TADF)
have
become
wildly
popular
as
next
generation
emitters
in
organic
light-emitting
diodes
(OLEDs),
but
since
2016,
received
significant
and
increasing
attention
photocatalysts.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(8), P. 4237 - 4352
Published: Jan. 24, 2023
The
emergence
of
modern
photocatalysis,
characterized
by
mildness
and
selectivity,
has
significantly
spurred
innovative
late-stage
C–H
functionalization
approaches
that
make
use
low
energy
photons
as
a
controllable
source.
Compared
to
traditional
strategies,
photocatalysis
paves
the
way
toward
complementary
and/or
previously
unattainable
regio-
chemoselectivities.
Merging
compelling
benefits
with
workflow
offers
potentially
unmatched
arsenal
tackle
drug
development
campaigns
beyond.
This
Review
highlights
photocatalytic
strategies
small-molecule
drugs,
agrochemicals,
natural
products,
classified
according
targeted
bond
newly
formed
one.
Emphasis
is
devoted
identifying,
describing,
comparing
main
mechanistic
scenarios.
draws
critical
comparison
between
established
ionic
chemistry
photocatalyzed
radical-based
manifolds.
aims
establish
current
state-of-the-art
illustrate
key
unsolved
challenges
be
addressed
in
future.
authors
aim
introduce
general
readership
functionalization,
specialist
practitioners
evaluation
methodologies,
potential
for
improvement,
future
uncharted
directions.
Accounts of Chemical Research,
Journal Year:
2021,
Volume and Issue:
54(10), P. 2518 - 2531
Published: May 6, 2021
ConspectusCarbon
dioxide
(CO2)
is
not
only
a
greenhouse
gas
and
common
waste
product
but
also
an
inexpensive,
readily
available,
renewable
carbon
resource.
It
important
one-carbon
(C1)
building
block
in
organic
synthesis
for
the
construction
of
valuable
compounds.
However,
its
utilization
challenging
owing
to
thermodynamic
stability
kinetic
inertness.
Although
significant
progress
has
been
achieved,
many
limitations
remain
this
field
with
regard
substrate
scope,
reaction
system,
activation
strategies.Since
2015,
our
group
focused
on
CO2
synthesis.
We
are
interested
vast
possibilities
radical
chemistry,
although
high
reactivity
radicals
presents
challenges
controlling
selectivity.
hope
develop
highly
useful
transformations
involving
by
achieving
balance
selectivity
under
mild
conditions.
Over
past
6
years,
we
along
other
experts
have
disclosed
radical-type
carboxylative
cyclizations
carboxylations
using
CO2.We
initiated
research
realizing
Cu-catalyzed
oxytrifluoromethylation
allylamines
heteroaryl
methylamines
generate
2-oxazolidones
various
precursors.
Apart
from
Cu
catalysis,
visible-light
photoredox
catalysis
powerful
method
achieve
efficient
cyclization.
In
these
cases,
single-electron-oxidation-promoted
C–O
bond
formation
between
benzylic
carbamates
key
step.Since
carboxylic
acids
exist
widely
natural
products
bioactive
drugs
serve
as
bulk
chemicals
industry,
realized
further
visible-light-promoted
construct
such
chemicals.
achieved
selective
umpolung
imines,
enamides,
tetraalkylammonium
salts,
oxime
esters
successive
single-electron-transfer
(SSET)
reduction.
Using
strategy,
dearomative
arylcarboxylation
indoles
CO2.
addition
incorporation
1
equiv
per
substrate,
recently
developed
photoredox-catalyzed
dicarboxylation
alkenes,
allenes,
(hetero)arenes
via
SSET
reduction,
which
allows
two
molecules
into
compounds
diacids
polymer
precursors.In
two-electron
CO2,
sought
new
strategies
realize
single-electron
Inspired
hypothetical
electron-transfer
mechanism
iron–sulfur
proteins,
visible-light-driven
thiocarboxylation
alkenes
catalytic
iron
salts
promoters.
The
in-situ-generated
Fe/S
complexes
likely
able
reduce
anion,
could
react
give
stabilized
radical.
Moreover,
charge-transfer
complex
(CTC)
thiolate
acrylate/styrene
hydrocarboxylation
generation
or
alkene
anion.
On
basis
novel
CTC,
organocatalytic
Hantzsch
ester
effective
reductant.
Chemical Science,
Journal Year:
2019,
Volume and Issue:
10(36), P. 8285 - 8291
Published: Jan. 1, 2019
The
concept
of
reductive
radical-polar
crossover
(RRPCO)
reactions
has
recently
emerged
as
a
valuable
and
powerful
tool
to
overcome
limitations
both
radical
traditional
polar
chemistry.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(18), P. 8122 - 8129
Published: April 20, 2020
The
first
example
of
visible-light-driven
reductive
carboarylation
styrenes
with
CO2
and
aryl
halides
in
a
regioselective
manner
has
been
achieved.
A
broad
range
iodides
bromides
were
compatible
this
reaction.
Moreover,
pyridyl
halides,
alkyl
even
chlorides
also
viable
method.
These
findings
may
stimulate
the
exploration
novel
Meerwein
arylation-addition
reactions
user-friendly
as
radical
sources
photocatalytic
utilization
CO2.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(29), P. 11918 - 11922
Published: April 29, 2020
Hierarchical
FeCoS2
-CoS2
double-shelled
nanotubes
have
been
rationally
designed
and
constructed
for
efficient
photocatalytic
CO2
reduction
under
visible
light.
The
synthetic
strategy,
engaging
the
two-step
cation-exchange
reactions,
precisely
integrates
two
metal
sulfides
into
a
tubular
heterostructure
with
both
of
shells
assembled
from
ultrathin
two-dimensional
(2D)
nanosheets.
Benefiting
distinctive
structure
composition,
hybrid
can
reduce
bulk-to-surface
diffusion
length
photoexcited
charge
carriers
to
facilitate
their
separation.
Furthermore,
this
expose
abundant
active
sites
enhancing
adsorption
surface-dependent
redox
harvest
incident
solar
irradiation
more
efficiently
by
light
scattering
in
complex
interior.
As
result,
these
hierarchical
exhibit
superior
activity
high
stability
photosensitized
deoxygenative
reduction,
affording
CO-generating
rate
28.1
μmol
h-1
(per
0.5
mg
catalyst).
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(45), P. 19956 - 19960
Published: July 23, 2020
Despite
the
great
potential
of
radical
chemistry
in
organic
synthesis,
N-heterocyclic
carbene
(NHC)-catalyzed
reactions
involving
intermediates
are
not
well
explored.
This
communication
reports
three-component
coupling
aroyl
fluorides,
styrenes
and
Langlois
reagent
(CF3
SO2
Na)
to
give
various
β-trifluoromethylated
alkyl
aryl
ketones
with
good
functional
group
tolerance
moderate
high
yields
by
cooperative
photoredox/NHC
catalysis.
The
alkene
acyltrifluoromethylation
proceeds
via
radical/radical
cross
ketyl
radicals
benzylic
C-radicals.
generated
SET
reduction
situ
formed
acylazolium
ions
whereas
derive
from
trifluoromethyl
addition
onto
styrenes.