The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(6), P. 4145 - 4155
Published: Feb. 28, 2024
The
environmental
benefits
of
molecular
oxygen
as
the
oxidizing
agent
in
oxidation
reactions
that
synthesize
fine
chemicals
cannot
be
overstated.
Increased
interest
developing
robust
photocatalysts
is
stimulated
by
fact
current
photocatalytic
transformation
boom
has
made
previously
inaccessible
synthetic
approaches
possible.
Motivated
enzymatic
catalysis,
employing
a
reusable
phenalenyl-based
photocatalyst,
we
have
successfully
developed
oxidative
dehydrogenation
utilizing
greener
oxidant.
Under
photoinduced
conditions,
different
types
saturated
N-heterocycles
and
alcohols
were
dehydrogenated.
versatility
this
bioinspired
protocol
demonstrated
wide
variety
N-heteroaromatics,
such
quinoline,
carbazole,
quinoxaline,
acridine,
indole
derivatives,
well
aldehydes
ketones,
synthesized.
Detailed
mechanistic
studies
validate
proposed
mechanism.
Fluorescence
lifetime
CV
experiments
revealed
crucial
role
water
on
efficiency
reaction.
present
also
provides
chemoselectivity
scalability,
leading
to
superior
results
allowing
for
functionalization
bioactive
molecules
at
late
stage
sustainable
manner.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(7), P. 4530 - 4537
Published: March 14, 2024
A
copper-catalyzed
method
for
the
dehydrogenation
of
various
nitrogen-containing
heterocycles
to
furnish
quinolines
and
indoles
has
been
developed.
range
1,2,3,4-tetrahydroquinolines
underwent
by
employing
2
mol
%
copper
complex
Cat
3
as
a
catalyst
using
O2
an
oxidant
at
120
°C
in
1,2-dichlorobenzene
afford
desired
quinolines.
The
enables
variety
indolines
presence
2,
10
TEMPO
additive
under
room
temperature
tetrahydrofuran
high
yields.
Mechanistic
studies
suggested
that
dehydrogenative
activity
is
ascribed
formation
copper(II)
active
species
from
copper(I)
complexes
oxidized
O2,
which
was
proved
high-resolution
mass
spectrometry
(HRMS).
reaction
proceeds
via
superoxide
radical
anion
(·O2–)
electron
paramagnetic
resonance
(EPR)
spectrometry.
In
situ
infrared
spectroscopy
revealed
dihydroquinoline
intermediate
formed
1,2,3,4-tetrahydroquinolines.
The
transition
metal
catalyzed
dehydrogenation
of
alcohols
to
carboxylate
salts
and
H2
is
an
attractive
tool
due
their
potential
use
as
LOHCs
(Liquid
Organic
Hydrogen
Carriers).
Still,
most
current
methods
encompass
harsh
conditions
two
steps
synthesis.
Herein,
we
describe
efficient
ruthenium(II)
hydrogen
production
from
benzylic
the
corresponding
benzyl
carboxylates
assisted
by
visible
light.
Our
photocatalytic
system
comprises
a
standalone
N-heterocyclic
carbene
based
piano
stool
ruthenium
complex
playing
dual
role,
harvesting
visible-light
enabling
generation
under
mild
in
aqueous
media.
We
report
the
first
example
of
photocatalytic
acceptorless
dehydrogenation
using
cationic
Eosin
Y
as
a
bifunctional
photocatalyst,
without
metal
catalysts
or
HAT
reagents.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 13, 2025
Switchable
selectivity
achieved
by
altering
reaction
conditions
within
the
same
photocatalytic
system
offers
great
advantages
for
sustainable
chemical
transformations
and
renewable
energy
conversion.
In
this
study,
we
investigate
an
efficient
methanol
dehydrogenation
with
controlled
varying
concentration
of
nickel
cocatalyst,
using
zinc
indium
sulfide
nanocrystals
as
a
semiconductor
photocatalyst,
which
enables
production
either
formaldehyde
or
ethylene
glycol
high
selectivity.
Control
experiments
revealed
that
is
initially
generated
can
serve
terminal
product
intermediate
in
producing
glycol,
depending
on
solution.
Mechanistic
studies
suggest
unique
role
ionic
additional
photoelectron
competitor
significantly
influence
selectivity,
alongside
its
well-established
function
hydrogen
evolution
cocatalyst
under
conditions.
The
demonstrated
switchable
provides
new
tool
diverse
products
from
methanol,
while
advancing
understanding
behavior
versatile
catalytic
performance.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Feb. 7, 2025
The
dehydrogenative
aromatisation
of
cyclohexanone
derivatives
has
had
a
transformative
influence
on
the
synthesis
aromatic
compounds
because
functional
groups
can
be
easily
introduced
at
desired
positions
via
classic
organic
reactions
without
being
limited
by
ortho-,
meta-
or
para-orientations.
However,
research
is
still
acceptorless
aromatisation,
especially
with
regard
to
nonprecious-metal
catalysts.
Ni
promising
candidate
catalyst
as
congener
Pd,
but
thermally
Ni-catalysed
not
been
reported
even
in
an
oxidative
manner
difficulty
β-hydride
elimination
and
fast
re-insertion
Ni–H
species.
Here,
we
report
CeO2-supported
Ni(0)
nanoparticle
for
derivatives.
This
widely
applicable
various
such
cyclohexanols,
cyclohexylamines,
N-heterocycles,
enamines
β-heteroatom-substituted
ketones.
Through
experiments,
demonstrate
that
present
reaction
was
achieved
concerted
catalysis
utilizing
metal
ensembles
unique
supported
Acceptorless
aromatization
cyclohexanones
advantageous
nickel
study
presents
method
broad
substrate
applicability,
nanoparticles.
Solar RRL,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 4, 2025
Single‐atom
catalysts
(SACs)
show
promise
because
of
their
efficient
use
precious
metals,
unique
coordination
and
electronic
structures,
excellent
tunability.
Photocatalysis
can
harvest
solar
energy
to
drive
energetically
unfavorable
reactions
under
mild
conditions,
offering
a
sustainable
alternative
energy‐intensive
reactions.
However,
the
efficiency
photocatalysis
is
limited
by
poor
spectrum
utilization
rapid
charge
recombination.
Integrating
single
atoms
into
semiconductor
photocatalysts
promising
route
address
these
limitations.
Mechanistic
understanding
single‐atom
crucial
for
developing
as
they
guide
effective
material
design.
This
work
provides
an
overview
current
knowledge
on
platinum
group
SACs
applied
photocatalytic
applications
with
focus
role
in
The
review
begins
summary
advantages
metal
well
common
structures.
A
concise
synthesis
methods
then
provided,
followed
comprehensive
characterization
SAC
structure,
photoelectronic
properties,
mechanisms
action.
Next,
improving
general
processes
specific
are
discussed.
Finally,
future
outlooks
development
included
further
advancements
field.
