Angewandte Chemie,
Год журнала:
2024,
Номер
136(27)
Опубликована: Апрель 23, 2024
Abstract
Homogeneous
electrocatalysts
can
indirect
oxidate
the
high
overpotential
substrates
through
single‐electron
transfer
on
electrode
surface,
enabling
efficient
operation
of
organic
electrosynthesis
catalytic
cycles.
However,
problems
this
chemistry
still
exist
such
as
dosage,
difficult
recovery,
and
low
efficiency.
Single‐atom
catalysts
(SACs)
exhibit
atom
utilization
excellent
activity,
hold
great
promise
in
addressing
limitations
homogeneous
catalysts.
In
view
this,
we
have
employed
Fe‐SA@NC
an
advanced
redox
mediator
to
try
change
situation.
was
synthesized
using
encapsulation‐pyrolysis
method,
it
demonstrated
remarkable
performance
a
range
reported
reactions,
construction
various
C−C/C−X
bonds.
Moreover,
potential
exploring
new
synthetic
method
for
electrosynthesis.
We
develop
electro‐oxidative
ring‐opening
transformation
cyclopropyl
amides.
reaction
system,
showed
good
tolerance
drug
molecules
with
complex
structures,
well
flow
electrochemical
syntheses
gram‐scale
transformations.
This
work
highlights
SACs
electrosynthesis,
thereby
opening
avenue
chemistry.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(45)
Опубликована: Сен. 12, 2023
Despite
widespread
use
of
the
deuterium
isotope
effect,
selective
labeling
chemical
molecules
remains
a
major
challenge.
Herein,
facile
and
general
electrochemically
driven,
organic
mediator
enabled
deuteration
styrenes
with
oxide
(D2
O)
as
economical
source
was
reported.
Importantly,
this
transformation
could
be
suitable
for
various
electron
rich
mediated
by
triphenylphosphine
(TPP).
The
reaction
proceeded
under
mild
conditions
without
transition-metal
catalysts,
affording
desired
products
in
good
yields
excellent
D-incorporation
(D-inc,
up
to
>99
%).
Mechanistic
investigations
means
experiments
cyclic
voltammetry
tests
provided
sufficient
support
transformation.
Notably,
method
proved
powerful
tool
late-stage
biorelevant
compounds.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(3)
Опубликована: Дек. 7, 2023
The
oxygen
evolution
reaction
(OER),
characterized
by
a
four-electron
transfer
kinetic
process,
represents
significant
bottleneck
in
improving
the
efficiency
of
hydrogen
production
from
water
electrolysis.
Consequently,
extensive
research
efforts
have
been
directed
towards
identifying
single-atom
electrocatalysts
with
exceptional
OER
performance.
Despite
comprehensive
understanding
mechanism,
its
application
to
other
valuable
synthetic
reactions
has
limited.
Herein,
we
leverage
MOOH
intermediate,
key
species
Mn-N-C
catalyst
(Mn-SA@NC),
which
can
be
cyclically
delivered
OER.
We
exploit
this
intermediate'
s
capability
facilitate
electrophilic
silane,
enabling
efficient
silane
oxidation
under
electrochemical
conditions.
SAC
electrocatalytic
system
exhibits
remarkable
performance
loadings
as
low
600
ppm
and
an
turnover
number
9132.
Furthermore,
catalytic
method
demonstrates
stability
10
mmol
flow
chemistry
setup.
By
serving
electrocatalyst,
Mn-SA@NC
drives
entire
reaction,
establishing
practical
Mn
SAC-catalyzed
organic
electrosynthesis
system.
This
synthesis
approach
not
only
presents
promising
avenue
for
utilization
but
also
highlights
potential
SACs
attractive
platform
investigations.
ACS Catalysis,
Год журнала:
2024,
Номер
14(6), С. 4211 - 4248
Опубликована: Март 5, 2024
Catalytic
transfer
hydrogenation
(CTH)
methodology
has
drawn
profound
attention
of
researchers
as
an
economical
and
environmentally
benign
alternate
to
conventional
method.
Unlike
method,
CTH
exhibits
better
reaction
efficiency
atom
economy,
it
makes
use
simple,
easily
accessible,
low-cost
hydrogen
sources.
Current
research
on
reactions
is
oriented
toward
the
development
non-noble-metal-based
catalysts
due
their
high
abundance
potential
large-scale
applicability.
In
this
Review,
different
organic
transformation
reactions,
such
nitroarenes,
nitriles,
alkenes,
alkynes,
carbonyl
compounds,
hydrogenolysis,
reductive
amination,
formylation
using
sources
have
been
summarized
comprehensively.
addition,
synthesis
strategies
heterogeneous
structure–activity
relationship
involving
metal–support
interaction,
single-atom
catalysis,
synergistic
effect
are
highlighted.
Furthermore,
optimization
parameters─such
temperature,
time,
solvents,
additives─for
enhancing
catalytic
activity
selectivity
product
discussed
in
detail.
This
Review
provides
detailed
insights
into
recent
progress
made
with
a
specific
focus
catalyst
development,
sources,
mechanistic
exploration.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(27)
Опубликована: Апрель 23, 2024
Homogeneous
electrocatalysts
can
indirect
oxidate
the
high
overpotential
substrates
through
single-electron
transfer
on
electrode
surface,
enabling
efficient
operation
of
organic
electrosynthesis
catalytic
cycles.
However,
problems
this
chemistry
still
exist
such
as
dosage,
difficult
recovery,
and
low
efficiency.
Single-atom
catalysts
(SACs)
exhibit
atom
utilization
excellent
activity,
hold
great
promise
in
addressing
limitations
homogeneous
catalysts.
In
view
this,
we
have
employed
Fe-SA@NC
an
advanced
redox
mediator
to
try
change
situation.
was
synthesized
using
encapsulation-pyrolysis
method,
it
demonstrated
remarkable
performance
a
range
reported
reactions,
construction
various
C-C/C-X
bonds.
Moreover,
potential
exploring
new
synthetic
method
for
electrosynthesis.
We
develop
electro-oxidative
ring-opening
transformation
cyclopropyl
amides.
reaction
system,
showed
good
tolerance
drug
molecules
with
complex
structures,
well
flow
electrochemical
syntheses
gram-scale
transformations.
This
work
highlights
SACs
electrosynthesis,
thereby
opening
avenue
chemistry.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Март 30, 2024
Abstract
Herein,
we
report
an
electroreduction
of
unactivated
alkyl
alkenes
enabled
by
[Fe]-H,
which
is
provided
through
the
combination
anodic
iron
salts
and
silane
generated
in
situ
via
cathodic
reduction,
using
H
2
O
as
H-source.
The
catalytic
amounts
Si-additive
work
H-carrier
from
to
generate
a
highly
active
species
under
continuous
electrochemical
conditions.
This
approach
shows
broad
substrate
scope
good
functional
group
compatibility.
In
addition
hydrogenation,
use
D
instead
provides
desired
deuterated
products
yields
with
excellent
D-incorporation
(up
>99%).
Further
late-stage
hydrogenation
complex
molecules
drug
derivatives
demonstrate
potential
application
pharmaceutical
industry.
Mechanistic
studies
are
performed
provide
support
for
proposed
mechanistic
pathway.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Май 7, 2024
Herein,
we
develop
a
straightforward,
metal-free,
and
acid-/base-free
electrochemical
C4-selective
C
-
H
deuteration
of
pyridine
derivatives
with
economic
convenient
D
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(15)
Опубликована: Фев. 7, 2024
Electrocatalytic
alkyne
semihydrogenation
under
mild
conditions
is
a
more
attractive
approach
for
alkene
production
than
industrial
routes
but
suffers
from
either
low
efficiency
or
high
energy
consumption.
Here,
we
describe
tandem
catalytic
concept
that
overcomes
these
challenges.
Component
(i),
which
can
trap
hydrogen
effectively,
partnered
with
component
(ii),
readily
release
hydrogenation,
to
enable
efficient
generation
of
active
on
(i)
at
overpotentials
and
timely
(i)-to-(ii)
spillover
facile
desorptive
hydrogenation
(ii).
We
examine
this
over
bicomponent
palladium-copper
catalysts
the
representative
2-methyl-3-butene-2-ol
(MBE)
2-methyl-3-butyne-2-ol
(MBY)
achieve
record
MBE
rate
1.44
mmol
h
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июль 17, 2024
Abstract
Electrocatalytic
alkynes
semi-hydrogenation
to
produce
alkenes
with
high
yield
and
Faradaic
efficiency
remains
technically
challenging
because
of
kinetically
favorable
hydrogen
evolution
reaction
over-hydrogenation.
Here,
we
propose
a
hierarchically
nanoporous
Cu
50
Au
alloy
improve
electrocatalytic
performance
toward
alkynes.
Using
Operando
X-ray
absorption
spectroscopy
density
functional
theory
calculations,
find
that
modulate
the
electronic
structure
Cu,
which
could
intrinsically
inhibit
combination
H*
form
H
2
weaken
alkene
adsorption,
thus
promoting
alkyne
hampering
Finite
element
method
simulations
experimental
results
unveil
catalysts
induce
local
microenvironment
abundant
K
+
cations
by
enhancing
electric
field
within
nanopore,
accelerating
water
electrolysis
more
H*,
thereby
conversion
As
result,
electrocatalyst
achieves
highly
efficient
94%
conversion,
100%
selectivity,
92%
over
wide
potential
window.
This
work
provides
general
guidance
rational
design
for
high-performance
transfer
catalysts.
