Chemical Reviews,
Год журнала:
2024,
Номер
124(21), С. 12264 - 12304
Опубликована: Окт. 23, 2024
Electrocatalysis
and
photocatalysis
have
been
the
focus
of
extensive
research
efforts
in
organic
synthesis
recent
decades,
these
powerful
strategies
provided
a
wealth
new
methods
to
construct
complex
molecules.
Despite
intense
efforts,
only
recently
has
there
significant
on
combined
use
two
modalities.
Nevertheless,
past
five
years
witnessed
rapidly
growing
interest
area
electrophotocatalysis.
This
hybrid
strategy
capitalizes
enormous
benefits
using
photons
as
reagents
while
also
employing
an
electric
potential
convenient
tunable
source
or
sink
electrons.
Research
this
topic
led
number
for
C-H
functionalization,
reductive
cross-coupling,
olefin
addition
among
others.
field
seen
broad
range
catalyst
types,
including
both
metal
organocatalysts.
Of
particular
note
work
with
open-shell
photocatalysts,
which
tend
comparatively
large
redox
potentials.
Electrochemistry
provides
means
generate
such
species,
making
electrophotocatalysis
particularly
amenable
intriguing
class
catalyst.
review
surveys
applied
synthesis,
organized
broadly
into
oxidative,
reductive,
neutral
transformations.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Март 30, 2024
Abstract
Electrochemical
research
often
requires
stringent
combinations
of
experimental
parameters
that
are
demanding
to
manually
locate.
Recent
advances
in
automated
instrumentation
and
machine-learning
algorithms
unlock
the
possibility
for
accelerated
studies
electrochemical
fundamentals
via
high-throughput,
online
decision-making.
Here
we
report
an
autonomous
platform
implements
adaptive,
closed-loop
workflow
mechanistic
investigation
molecular
electrochemistry.
As
a
proof-of-concept,
this
autonomously
identifies
investigates
EC
mechanism,
interfacial
electron
transfer
(
E
step)
followed
by
solution
reaction
C
step),
cobalt
tetraphenylporphyrin
exposed
library
organohalide
electrophiles.
The
generally
applicable
accurately
discerns
mechanism’s
presence
amid
negative
controls
outliers,
adaptively
designs
desired
conditions,
quantitatively
extracts
kinetic
information
step
spanning
over
7
orders
magnitude,
from
which
insights
into
oxidative
addition
pathways
gained.
This
work
opens
opportunities
discoveries
self-driving
electrochemistry
laboratories
without
manual
intervention.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(31), С. 21960 - 21967
Опубликована: Июль 23, 2024
Oxygen-atom
transfer
reactions
are
a
prominent
class
of
synthetic
redox
that
often
use
high-energy
oxygen-atom
donor
reagents.
Electrochemical
methods
can
bypass
these
reagents
by
using
water
as
the
source
oxygen
atoms
through
pathways
involving
direct
or
indirect
(mediated)
electrolysis.
Here,
manganese
porphyrins
and
related
mediators
shown
to
be
effective
molecular
electrocatalysts
for
selective
oxidation
thioethers
sulfoxides,
without
overoxidation
sulfone.
The
proceed
proton-coupled
Mn
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(31)
Опубликована: Май 16, 2024
Aryl
radicals
play
a
pivotal
role
as
reactive
intermediates
in
chemical
synthesis,
commonly
arising
from
aryl
halides
and
diazo
compounds.
Expanding
the
repertoire
of
sources
for
radical
generation
to
include
abundant
stable
organoboron
reagents
would
significantly
advance
chemistry
broaden
their
reactivity
profile.
While
traditional
approaches
utilize
stoichiometric
oxidants
or
photocatalysis
generate
these
reagents,
electrochemical
conditions
have
been
largely
underexplored.
Through
rigorous
mechanistic
investigations,
we
identified
fundamental
challenges
hindering
generation.
In
addition
high
oxidation
potentials
aromatic
compounds,
electrode
passivation
through
grafting,
homocoupling
radicals,
decomposition
issues
were
identified.
We
demonstrate
that
pulsed
electrosynthesis
enables
selective
efficient
by
mitigating
challenges.
Our
discoveries
facilitated
development
first
conversion
potassium
trifluoroborate
salts
into
C-P
bonds.
This
sustainable
straightforward
oxidative
approach
exhibited
broad
substrate
scope,
accommodating
various
heterocycles
chlorides,
typical
substrates
transition-metal
catalyzed
cross-coupling
reactions.
Furthermore,
extended
this
methodology
form
C-Se,
C-Te,
C-S
bonds,
showcasing
its
versatility
potential
bond
formation
processes.
Chemical Reviews,
Год журнала:
2024,
Номер
124(21), С. 12264 - 12304
Опубликована: Окт. 23, 2024
Electrocatalysis
and
photocatalysis
have
been
the
focus
of
extensive
research
efforts
in
organic
synthesis
recent
decades,
these
powerful
strategies
provided
a
wealth
new
methods
to
construct
complex
molecules.
Despite
intense
efforts,
only
recently
has
there
significant
on
combined
use
two
modalities.
Nevertheless,
past
five
years
witnessed
rapidly
growing
interest
area
electrophotocatalysis.
This
hybrid
strategy
capitalizes
enormous
benefits
using
photons
as
reagents
while
also
employing
an
electric
potential
convenient
tunable
source
or
sink
electrons.
Research
this
topic
led
number
for
C-H
functionalization,
reductive
cross-coupling,
olefin
addition
among
others.
field
seen
broad
range
catalyst
types,
including
both
metal
organocatalysts.
Of
particular
note
work
with
open-shell
photocatalysts,
which
tend
comparatively
large
redox
potentials.
Electrochemistry
provides
means
generate
such
species,
making
electrophotocatalysis
particularly
amenable
intriguing
class
catalyst.
review
surveys
applied
synthesis,
organized
broadly
into
oxidative,
reductive,
neutral
transformations.
