Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 10, 2025
Carbonyl-containing
compounds
serve
as
essential
building
blocks
in
various
synthetic
processes.
However,
due
to
the
high
bond
energy
of
C═O
double
bond,
traditional
deoxygenation
methods
often
require
harsh
conditions
or
toxic
reagents.
Direct
carbonyl
deoxygenative
coupling
aldehydes
and
ketones
is
still
challenging
under
mild
conditions.
Herein
we
report
successful
establishment
an
electroreductive
strategy
utilizing
aromatic
carbonyls
terephthalonitrile.
A
key
component
our
approach
use
closo-boranes,
specifically
(Et4N)2B10H10,
which
situ
deoxidant
by
single-electron
oxidation.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(45)
Published: June 16, 2023
Abstract
Electrochemistry
utilizes
electrons
as
a
potent,
controllable,
and
traceless
alternative
to
chemical
oxidants
or
reductants,
typically
offers
more
sustainable
option
for
achieving
selective
organic
synthesis.
Recently,
the
merger
of
electrochemistry
with
readily
available
electrophiles
has
been
recognized
viable
increasingly
popular
methodology
efficiently
constructing
challenging
C−C
C‐heteroatom
bonds
in
manner
complex
molecules.
In
this
mini‐review,
we
have
systematically
summarized
most
recent
advances
electroreductive
cross‐electrophile
coupling
(eXEC)
reactions
during
last
decade.
Our
focus
on
electrophiles,
including
aryl
alkyl
(pseudo)halides,
well
small
molecules
such
CO
2
,
SO
D
O.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(45)
Published: Sept. 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.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(4), P. 2351 - 2357
Published: Jan. 17, 2024
Cross-coupling
catalysts
typically
react
and
unite
functionally
distinct
partners
via
sequential
inner-sphere
elementary
steps:
coordination,
migratory
insertion,
reductive
elimination,
etc.
Here,
we
report
a
single
catalyst
that
cross-couples
styrenes
benzyl
bromides
iterative
outer-sphere
metal–ligand-carbon
interactions.
Each
partner
forms
stabilized
radical
intermediate,
yet
heterocoupled
products
predominate.
The
system
is
redox-neutral
and,
thus,
avoids
exogenous
oxidants,
resulting
in
simple
scalable
conditions.
Numerous
variations
of
alkene
hydrobenzylation
are
made
possible,
including
access
to
the
privileged
heterodibenzyl
(1,2-diarylethane)
motif
challenging
quaternary
carbon
variants.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(16), P. 1921 - 1930
Published: April 7, 2023
Comprehensive
Summary
The
radical‐mediated
reductive
functionalization
of
aryl
halides
has
been
extensively
studied.
However,
the
related
intermolecular
1,2‐diarylation
alkenes,
using
as
radical
sources,
remains
unexplored.
Herein,
a
new
electrophotocatalytic
alkenes
is
reported
and
cyanoaromatics
to
produce
polyarylated
alkanes.
Using
synergistic
cathodic
reduction
visible‐light
photoredox
catalysis,
various
electron‐rich
electron‐deficient
are
combined
with
characterize
broad
substrate
scope,
excellent
functional
group
compatibility,
selectivity
this
reaction.
Mechanistic
investigations
reveal
that
reaction
may
proceed
via
process
initiated
by
generation
radicals
from
terminated
radical‐radical
coupling
cyanoaromatic
anions.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(12), P. 2440 - 2444
Published: March 19, 2024
An
iodoarene-driven
electroreductive
remote
C(sp3)–H
arylation
of
unsymmetrical
1-(o-iodoaryl)alkyl
ethers
with
cyanoarenes
for
the
site
selective
synthesis
α-(hetero)aryl
is
developed.
With
introduction
as
both
aryl
sources
and
electron
transfer
mediators,
this
method
includes
an
strategy
to
enable
regiocontrollable
formation
two
new
bonds,
one
C(sp2)–H
bond,
C(sp2)–C(sp3)
in
a
single
reaction
step
through
sequence
halogen
atom
(XAT),
hydrogen
(HAT),
radical–radical
coupling,
decyanation.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(15), P. 4318 - 4342
Published: Jan. 1, 2024
This
review
primarily
focuses
on
the
generation
of
aryl
radicals
via
an
electroreduction
strategy,
and
systematically
elaborates
synthetic
applications,
scope,
limitations
substrates.
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.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Dec. 13, 2023
An
electroreductive
strategy
for
radical
hydroxyl
fluorosulfonylation
of
alkenes
with
sulfuryl
chlorofluoride
and
molecular
oxygen
from
air
is
described.
This
mild
protocol
displays
excellent
functional
group
compatibility,
broad
scope,
good
scalability,
providing
convenient
access
to
diverse
β-hydroxy
sulfonyl
fluorides.
These
fluoride
products
can
be
further
converted
valuable
aliphatic
fluorides,
β-keto
β-alkenyl
Further,
some
these
showed
inhibitory
activity
against
Botrytis
cinerea
or
Bursaphelenchus
xylophilus,
which
could
useful
potent
agrochemical
discovery.
Preliminary
mechanistic
studies
indicate
that
this
transformation
achieved
through
rapid
O2
interception
by
the
alkyl
subsequent
reduction
peroxy
radical,
outcompete
other
side
reactions
such
as
chlorine
atom
transfer,
hydrogen
Russell
fragmentation.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(21), P. 4427 - 4432
Published: May 17, 2024
2,3-Diaryl
propanoic
acids
are
important
structures
as
a
result
of
their
widespread
presence
in
numerous
bioactive
compounds.
However,
the
limitations
existing
synthetic
techniques
include
requirement
for
costly
catalysts
and
limited
substrates.
Here,
we
developed
novel
electroreductive
arylcarboxylation
alkenes
with
CO2
based
on
radical–polar
crossover
pathway
assisted
by
easily
accessible
dimethyl
terephthalate
reductive
mediator.
This
method
will
provide
an
efficient
strategy
synthesis
2,3-diarylpropanoic
acids.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(29), P. 11418 - 11427
Published: Jan. 1, 2024
An
environmentally
friendly
electroreduction
approach
is
disclosed
for
site-specific
introduction
of
deuterium
via
anti-Markovnikov
selective
deuteroarylation
alkenes
and
aryl
iodides
with
bipyridine
as
a
mediator
D
2
O
‘D’
source.
