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.
Angewandte Chemie,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 10, 2025
Abstract
Electrochemical
synthesis
offers
a
powerful
and
sustainable
alternative
to
conventional
chemical
manufacturing
techniques.
The
direct
selective
electrohydrogenation
of
olefins
has
enormous
potential
applicability;
however,
this
reactivity
not
been
sufficiently
demonstrated.
Herein,
we
show
that
an
efficient
Pt‐based
electrocatalyst
from
commercially
available
PtCl
2
can
promote
such
transformations.
This
approach
enables
be
electrohydrogenated
(often
below
−3.0
V
vs.
Ag/AgCl)
at
high
current
density
(
J
Geo
up
133
mA
cm
−2
)
using
protons
electrons
as
the
hydrogen
source.
reaction
exhibits
broad
functional
group
compatibility,
requires
low
catalyst
loading,
affords
diverse
series
valuable
molecules
(more
than
60
examples)
with
chemoselectivity.
In
addition,
highly
regioselective
electrocatalytic
hydrogenation
(r.r.
>
19:1)
is
demonstrated
2,2′‐bipyridine.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 24, 2025
A
photoredox/nickel
dual
catalytic
system
was
developed
for
the
three-component
1,2-carboalkynylation
of
alkenes.
This
redox-neutral
protocol
enables
efficient
and
divergent
synthesis
aliphatic
alkynes
in
high
yields
with
excellent
regioselectivity,
using
readily
available
starting
materials.
The
resulting
adducts
can
be
transformed
into
terminal
alkynes,
facilitating
diverse
downstream
transformations.
Mechanistic
studies
were
performed
to
elucidate
preferred
pathway
this
alkene
difunctionalization
process.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 21, 2025
An
acid
or
hydrogen
gas-free
electrochemical
protocol
is
established
for
the
hydrogenation
of
strained
rings
(cyclopropane
and
cyclobutane)
at
room
temperature
atmospheric
pressure.
The
mechanistic
study
revealed
that
reaction
was
initiated
via
reduction
carbonyl
group.
methodology
highly
specific
toward
such
as
cyclopropane
cyclobutane,
which
exhibit
broad
functional
group
tolerance.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 21, 2025
Transition-metal
hydrides
stand
as
indispensable
intermediates
in
both
energy
conversion
and
organic
synthesis.
Their
electrochemical
generation
represents
a
compelling
sustainable
approach,
enabling
precise
control
over
the
reactivity
expanding
scope
of
electrocatalytic
hydrogenation
isomerization.
However,
major
challenge
Ni-catalyzed
is
competing
hydrogen
evolution
reaction
(HER),
which
has
led
to
various
innovative
strategies
aimed
at
circumventing
Ni-H
formation.
Here,
we
pursued
an
alternative
approach
by
designing
bifunctional
ligand
with
pendant
amine
moiety
promote
This
design
enabled
selective
(semi)hydrogenation
diverse
range
substrates,
including
terminal
internal
alkynes,
alkenes,
aldehydes,
achieving
unprecedented
substrate
scope.
Remarkably,
also
demonstrated
tunable
positional
selectivity
for
olefin
isomerization
employing
different
types
proton
sources.
Our
method
exhibits
excellent
functional
group
tolerance,
streamlining
access
pharmaceuticals
their
derivatives.
Computational
studies
revealed
crucial,
noninnocent
role
source
modulating
metal
hydride
selectivity,
either
through
bonding,
direct
protonation
amine,
or
facilitation
protodemetalation.
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.
