The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 26, 2024
In
this
work,
a
switchable
synthesis
of
β-ketosulfone
and
α-chloroketone
through
radical
difunctionalization
alkenes
is
reported.
The
transformation
works
well
under
iron
peroxo
species/photoredox
dual
catalysis
an
open-flask
atmosphere,
the
reaction
highlighted
with
good
yields
broad
scope.
Mechanism
studies
show
that
initiated
by
formal
[4
+
2]
cyclization
sulfonyl
in
regioselective
manner.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 4665 - 4680
Published: March 5, 2025
Transition
metal
catalysis
is
an
indispensable
tool
for
organic
synthesis
that
has
been
harnessed,
modulated,
and
perfected
many
decades
by
careful
selection
of
centers
ligands,
giving
rise
to
synthetic
methods
with
unparalleled
efficiency
chemoselectivity.
Recent
developments
have
demonstrated
how
light
irradiation
can
also
be
recruited
as
a
powerful
dramatically
alter
the
outcome
catalytic
reactions,
providing
access
innovative
pathways
remarkable
potential.
In
this
context,
adoption
photochemical
conditions
mainstream
strategy
drive
reactions
unveiled
exciting
opportunities
exploit
rich
excited-state
framework
transition
metals
applications.
This
Perspective
examines
advances
in
application
complexes
standalone
photocatalysts,
exploiting
innate
reactivity
their
excited
states
beyond
common
use
photoredox
catalysts.
An
account
relevant
examples
dissected
provide
discussion
on
electronic
reorganization,
orbitals
involved,
associated
different
types
states.
analysis
aims
practitioners
fundamental
principles
guiding
strategies
understand,
design,
apply
light-activation
homogeneous
synthesis.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
A
photoinduced
iron-catalyzed
fluoroalkylation-peroxidation
of
activated
and/or
unactivated
alkenes
with
fluoroalkyl
carboxylic
acids
and
hydroperoxide
has
been
realized.
ChemistrySelect,
Journal Year:
2025,
Volume and Issue:
10(4)
Published: Jan. 1, 2025
Abstract
Owing
to
its
possible
advantages
for
the
environment
and
economy,
photoredox
catalysis
of
organic
processes
fueled
by
iron
has
garnered
a
lot
interest
recently.
The
potential
photo‐induced
single‐electron
transfer
(SET)
events
occurring
outside
sphere
is
now
well
acknowledged.
Currently,
focus
shifted
newly
discovered
photoactivation
method
that
based
on
an
inner‐sphere
mode
reactivity
caused
population
visible‐light‐induced
homolysis
(VLIH)
states.
VLIH
activation,
in
contrast
photoredox,
specific
complexes,
offers
distinct
profiles,
does
not
require
redox
potentials
coincide.
These
attractive
properties
have
prompted
development
strategies
use
this
blueprint
manufacture
highly
reactive
open‐shell
species
mild
environments.
purpose
contribution
promote
novel
synthetic
techniques
sustainable
chemical
transformations
offer
educational
instrument
understanding
evolving
idea.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 31, 2025
Trifluoromethylation
is
a
key
transformation
in
drug
and
agrochemical
synthesis,
yet
current
reagents
often
suffer
from
high
cost,
low
atom
economy,
scalability.
Trifluoroacetate
derivatives
represent
ideal
as
they
are
highly
abundant
cheap,
but
their
very
positive
one
electron
oxidation
potential
(∼2.3
V
vs
NHE)
hampers
widespread
use
photoredox
catalysis.
Indeed,
at
these
potentials,
selectively
oxidizing
trifluoroacetate
over
reaction
solvent
or
partner
substrates
becomes
challenging.
Herein,
we
present
novel
approach
that
circumvents
limitations
through
the
of
pentacationic
Ir(III)
photosensitizer
forms
strong
1:1
ion-pair
with
acetonitrile
(Keq
=
6
×
104
M–1).
This
formation
enables
rapid
efficient
photooxidation
∼90
ps
without
significant
substrate
oxidation,
indicated
by
femtosecond
nanosecond
UV–visible
transient
absorption
spectroscopy.
The
CF3•
radicals
so
generated
shown
to
trifluoromethylate
range
substrates,
including
aromatic
compounds,
heterocycles,
natural
products
pharmaceutically
relevant
products,
moderate
yields
(20–60%).
Control
experiments
reveal
ion-pairing
crucial
for
successful
generation
photosensitizers
oxidize
forming
ion
pairs
were
ineffective
trifluoromethylation.
probably
originates
more
thermodynamically
accessible
outcompeting
diffusional
oxidation.
was
further
exemplified
allow
functionalization
variety
perfluoroalkyl
groups
different
chain
lengths.
reported
herein
could
also
be
used
removal
and/or
substances
(PFAS),
called
"forever
chemicals",
have
recently
raised
environmental
health
concern.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 30, 2024
Bis(trifluoromethyl)carbinols
are
valuable
pharmacophores,
yet
their
synthesis
is
challenging,
largely
due
to
a
scarcity
of
safe
and
effective
bis(trifluoromethyl)carbinolation
reagents.
Here,
we
realized
the
hydrobis(trifluoromethyl)carbinolation
alkenes,
utilizing
stable
readily
accessible
2,2-bis(trifluoromethyl)glycolic
acid
as
source
both
bis(trifluoromethyl)carbinol
unit
hydrogen
atom.
This
process
leverages
photoinduced
Fe-LMCT-enabled
radical
decarboxylation
that
generates
key
intermediate.
Our
mild
protocol
facilitates
diverse
range
alkyl
bis(trifluoromethyl)carbinols,
including
structurally
complex
molecules
with
pharmaceutical
relevance.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
Dual
ligand-enabled
iron
photocatalysis
for
the
conversion
of
all
kinds
halogen-containing
carboxylates
(C
n
X
m
COO
−
,
X:
F,
Cl,
Br)
to
C
radicals
is
disclosed
chloro/fluoro-polyhaloalkylation
non-activated
alkenes.
Journal of Materials Chemistry A,
Journal Year:
2024,
Volume and Issue:
12(35), P. 23897 - 23909
Published: Jan. 1, 2024
A
copper
single-atom
catalyst
(Cu
1
@C
3
N
5
-1)
has
been
developed
for
photocatalytic
oxidation
of
biomass-derived
furfural
and
5-hydroxymethylfurfural
to
obtain
maleic
anhydride.
O
2
·O
−
play
a
synergetic
role
during
the
reaction.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 20, 2024
In
recent
years,
visible
light-induced
ligand-to-metal
charge
transfer
(LMCT)
has
emerged
as
an
attractive
approach
for
synthesizing
a
range
of
functionalized
molecules.
Compared
to
conventional
photoredox
reactions,
photoinduced
LMCT
activation
does
not
depend
on
redox
potential
and
offers
diverse
reaction
pathways,
making
it
particularly
suitable
the
inert
bonds
functional
modification
complex
organic
This
review
highlights
indispensable
role
in
synthetic
chemistry,
with
focus
advancements
LMCT-mediated
hydrogen
atom
(HAT),
C-C
bond
cleavage,
decarboxylative
transformations,
radical
ligand
(RLT)
reactions.
