Chemical Society Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 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.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(29)
Published: March 18, 2024
Abstract
Organoalkali
compounds
have
undergone
a
far‐reaching
transformation
being
coupling
partner
to
mediator
in
unusual
organic
conversions
which
finds
its
spot
the
field
of
sustainable
synthesis.
Transition‐metal
catalysis
has
always
been
priority
C(
sp
3
)−H
bond
functionalization,
however
alternatively,
recent
times
this
seriously
challenged
by
earth‐abundant
alkali
metals
and
their
complexes
arriving
at
new
organometallic
reagents.
In
line,
importance
MN(SiMe
)
2
(M=Li,
Na,
K
&
Cs)
reagent
revived
functionalization
over
years
synthesis
is
showcased
minireview.
with
higher
reactivity,
enhanced
stability,
bespoke
cation‐π
interaction
shown
eye‐opening
mediated
processes
such
as
)−C(
cross‐coupling,
radical‐radical
aminobenzylation,
annulation,
aroylation,
other
transformations
utilize
readily
available
petrochemical
feedstocks.
This
article
also
emphasizes
reactivity
unreactive
robust
C−X
(X=O,
N,
F,
C)
cleavage
reactions
that
occurred
alongside
functionalization.
Overall,
review
encourages
community
exploit
untapped
potential
inspires
them
take
up
subject
even
greater
heights.
Beilstein Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
20, P. 2500 - 2566
Published: Oct. 9, 2024
With
the
resurgence
of
electrosynthesis
in
organic
chemistry,
there
is
a
significant
increase
number
routes
available
for
late-stage
functionalization
(LSF)
drugs.
Electrosynthetic
methods,
which
obviate
need
hazardous
chemical
oxidants
or
reductants,
offer
unprecedented
control
reactions
through
continuous
variation
applied
potential
and
possibility
combination
with
photochemical
processes.
This
capability
substantial
advantage
performing
electrochemical
photoelectrochemical
LSF.
Ultimately,
these
protocols
are
poised
to
become
vital
component
medicinal
chemist's
toolkit.
In
this
review,
we
discuss
that
have
been
demonstrated
be
applicable
LSF
pharmaceutical
drugs,
their
derivatives,
natural
substrates.
We
present
analyze
representative
examples
illustrate
electrochemistry
photoelectrochemistry
valuable
molecular
scaffolds.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(5), P. 994 - 999
Published: Jan. 30, 2024
An
electroreductive
cross-electrophile
coupling
protocol
was
developed
for
the
construction
of
valuable
1,3-dienes
from
vinyl
bromides.
Furthermore,
this
scalable
method
can
also
be
used
to
forge
complex
[4
+
2]
cycloadducts
in
a
one-pot
manner.
One
most
important
advantages
green
and
sustainable
is
situ
release
nickel
catalyst
inexpensive
electrodes
without
addition
extra
harmful
metal
catalysts
reductant.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: March 8, 2025
Interfacial
photoelectrochemistry
at
photoanodes
has
been
extensively
researched
for
solar
energy
conversion,
but
its
application
the
production
of
high-value-added
chemical
compounds
in
organic
chemistry
still
presents
challenges.
Herein,
we
report
photoelectrocatalytic
Cl-mediated
C(sp3)–H
aminomethylation
alkanes
with
self-developed
and
reusable
BiVO4
photoanodes.
The
swift
condensation
aniline
aldehydes,
along
decrease
electricity
input
by
photogenerated
holes
photoanodes,
work
together
to
prevent
excessive
oxidation
aniline,
leading
high
yields
desired
product.
Mechanistic
experiments
demonstrate
that
Cl-
ions,
as
key
mediators,
could
be
attracted
oxidized
form
Cl2.
This
is
followed
light-promoted
homolytic
cleavage
Cl2,
generating
Cl
radicals
efficiently
abstract
hydrogen
atoms
from
hydrocarbons.
opens
an
avenue
interfacial
photoelectrochemical
synthesis
demonstrates
a
potential
method
optimizing
conversion
into
fuels.
A
stable
recyclable
photoelectrode
material
was
developed
efficient
hydrocarbons
cell,
which
provides
promising
fuel
conversion.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(51), P. 9237 - 9242
Published: Dec. 14, 2023
With
cyanopyridines
and
alkyl
bromides
as
coupling
partners,
an
electrochemically
driven
C4-selective
decyanoalkylation
has
been
established
to
access
diverse
4-alkylpyridines
in
one
step.
The
reaction
proceeds
through
the
single
electron
reduction/radical–radical
tandem
process
under
mild
electrolytic
conditions,
achieving
cleavage
of
C(sp2)–CN
bond
formation
C(sp3)–C(sp2).
practicality
this
protocol
is
illustrated
by
no
sacrificial
anodes,
a
broad
substrate
scope,
gram-scale
synthesis.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: April 4, 2024
Abstract
Cross-dehydrogenative
coupling
of
C(sp
3
)-H
bonds
is
an
ideal
approach
for
)-C(sp
)
bond
construction.
However,
conventional
approaches
mainly
rely
on
a
single
activation
mode
by
either
stoichiometric
oxidants
or
electrochemical
oxidation,
which
would
lead
to
inferior
selectivity
in
the
reaction
between
similar
bonds.
Herein
we
describe
our
development
paired
electrocatalysis
strategy
access
unconventional
cross-dehydrogenative
alcoholic
α
with
allylic
(or
benzylic)
C-H
bonds,
combines
hydrogen
evolution
catalysis
hydride
transfer
catalysis.
To
maximize
synergistic
effect
catalyst
combinations,
HER
pentacoordinated
Co-salen
disclosed.
The
displays
large
redox-potential
gap
(1.98
V)
and
suitable
redox
potential.
With
optimized
combination,
protocol
features
chemoselectivity
(C-C
vs
.
C-O
coupling),
excellent
functional
group
tolerance
(84
examples),
valuable
byproduct
(hydrogen),
high
regio-
site-selectivity.
A
plausible
mechanism
also
proposed
rationalize
experimental
observations.
