The Strategies towards Electrochemical Generation of Aryl Radicals
Chemistry - A European Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 16, 2024
The
advancement
in
electrochemical
techniques
has
unlocked
a
new
path
for
achieving
unprecedented
oxidations
and
reductions
of
aryl
radical
precursors
controlled
selective
manner.
This
approach
facilitates
the
construction
aromatic
carbon-carbon
carbon-heteroatom
bonds.
In
light
green
merits
growing
importance
this
technique
chemistry,
review
aims
to
provide
an
overview
recent
advance
generation
radicals
organized
by
precursor
type,
with
focus
on
substrate
scope,
limitation,
underlying
mechanism,
thereby
inspiring
future
work
generation.
Язык: Английский
Electroreduction strategy: a sustainable tool for the generation of aryl radicals
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(15), С. 4318 - 4342
Опубликована: Янв. 1, 2024
This
review
primarily
focuses
on
the
generation
of
aryl
radicals
via
an
electroreduction
strategy,
and
systematically
elaborates
synthetic
applications,
scope,
limitations
substrates.
Язык: Английский
Electroreductive Cross-Coupling Reactions: Carboxylation, Deuteration, and Alkylation
Accounts of Chemical Research,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 13, 2024
ConspectusElectrochemistry
has
been
used
as
a
tool
to
drive
chemical
reactions
for
more
than
two
centuries.
With
the
help
of
an
electrode
and
power
source,
chemists
are
provided
with
system
whose
potential
can
be
precisely
dialed
in.
The
theoretically
infinite
redox
range
renders
electrochemistry
capable
oxidizing
or
reducing
some
most
tenacious
compounds.
Indeed,
electroreduction
offers
alternative
generating
highly
active
intermediates
from
electrophiles
(e.g.,
halides,
alkenes,
etc.)
in
organic
synthesis,
which
untouchable
traditional
reduction
methods.
Meanwhile,
reductive
coupling
extensively
utilized
both
industrial
academic
settings
due
their
ability
swiftly,
accurately,
effectively
construct
C–C
C–X
bonds,
present
innovative
approaches
synthesizing
complex
molecules.
Nonetheless,
its
application
is
constrained
by
several
inherent
limitations:
(a)
requirement
stoichiometric
quantities
agents,
(b)
scarce
activation
strategies
inert
substrates
high
potentials,
(c)
incomplete
mechanistic
elucidation,
(d)
challenges
isolation
intermediates.
merging
represents
attractive
approach
address
above
limitations
synthesis
seen
increasing
use
synthetic
community
over
past
few
years.Since
2020,
our
group
dedicated
developing
electroreductive
cross-coupling
using
readily
available
small
molecules,
such
arenes,
CO2,
D2O,
value-added
products.
Electroreductive
chemistry
versatile
powerful
capacity
precise
selectivity
control,
allowed
us
develop
three
electrochemical
modes
lab:
(1)
An
economically
advantageous
direct
(EDR)
strategy
that
emphasizes
efficiency,
achieves
atom
utilization,
minimizes
unnecessary
atomic
waste.
(2)
A
class
organo-mediated
(EOMR)
methods
controlling
reaction
pathways.
This
allows
modulation
processes
enhance
efficiency
selectivity.
(3)
metal-catalyzed
(EMCR)
method
enables
selective
functionalization
specific
bonds
functional
groups
under
mild
conditions,
thereby
occurrence
side
reactions.
We
commenced
studies
establishing
organic-mediator-promoted
carboxylation
aryl
alkyl
halides.
was
then
employed
arylcarboxylation
simple
styrenes
halides
manner.
electrolysis
arenes
epoxides
CO2
carboxyl
source
achieved.
Moreover,
through
adjustment
we
successfully
accomplished
deuteration
olefins,
unactivated
enabling
efficient
formation
D-labeled
Finally,
building
on
previous
understanding
developed
series
alkylation
enable
C(sp3)–C(sp3)
Язык: Английский
Organo-electroreduction enables arylcarboxylation of styrenes
Science China Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 27, 2024
Язык: Английский
Organo-mediator enabled electrochemical transformations
Chemical Society Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
highlights
organo-mediators
that
enable
electrochemical
reactions
via
outer-sphere
electron
transfer
(ET),
offering
advantages
such
as
availability,
tunability,
and
simplified
post-processing
compared
to
direct
electrolysis.
Язык: Английский
Alkene Carboxy-Alkylation via CO2•–
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(51), С. 35035 - 35042
Опубликована: Дек. 12, 2024
Herein,
we
introduce
a
new
platform
for
alkene
carboxy-alkylation.
This
reaction
is
designed
around
CO
Язык: Английский
The Electrosynthesis of Highly Encumbered Biaryls from Aryl o-Iodobenzyl Ethers by a Radical to Polar Crossover Sequence.
Chemical Communications,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Highly
encumbered
2,2',6-tri-
and
2,2',6,6'-tetra-substituted
biaryls
are
readily
prepared
from
aryl
ortho-iodobenzyl
ethers
through
mediated
cathodic
reduction
under
flow.
The
reaction
proceeds
via
the
stepwise
transfer
of
two
electrons:
first
to
induce
loss
iodide
a
radical
cyclisation,
second
polar
fragmentation.
Язык: Английский
Electrochemical β-selective silylcarboxylation of styrenes with CO2
Science Bulletin,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 1, 2025
Язык: Английский
Visible-Light-Induced Arylcarboxylation of Activated Alkenes with Aryl Halides and Oxalate Enabled by Electron Donor–Acceptor Complex Formation
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 29, 2025
Simultaneous
construction
of
two
new
C-C
bonds
in
the
alkene
substrates
regioselectively
is
significantly
challenging.
Herein,
we
report
an
unprecedented
regioselective
arylcarboxylation
strategy
activated
alkenes
with
readily
available
aryl
halides
and
tetrabutylammonium
oxalate
as
reductant
C1
source
under
visible-light-induced
conditions.
The
reaction
proceeds
smoothly
to
access
various
carboxylic
acids
absence
any
catalysts,
additives,
metal
promoters,
or
pre-established
CO2
atmosphere.
electron
donor-acceptor
(EDA)
complex
formed
between
stoichiometric
amounts
trigger
single-electron
reduction
relay
process
after
irradiation
visible
light.
situ
generated
oxalic
radical
anion
species
undergoes
homolysis
bond
releases
potent
source,
respectively,
facilitate
reductive
carboxylation.
Язык: Английский
Remote C(sp3)–H Carboxylation with CO2 via Visible-Light-Catalyzed 1,5-Hydrogen Atom Transfer
Organic Letters,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 13, 2024
The
direct
carboxylation
of
C(sp3)–H
bonds
with
CO2
represents
a
challenging
but
highly
attractive
strategy
in
organic
synthesis.
In
this
study,
we
presented
visible-light-catalyzed
for
carboxylating
remote
via
aryl
radical
induced
1,5-hydrogen
atom
transfer.
This
transformation
involves
generating
alkyl
radicals
transfer
from
radicals,
forming
carbanions
as
key
intermediates,
and
subsequent
nucleophilic
attack
CO2,
thereby
enabling
access
to
variety
tertiary
quaternary
carboxylic
acids
moderate
good
yields.
Язык: Английский