Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(22), P. 4390 - 4419
Published: Jan. 1, 2024
The
merger
of
organic
electrosynthesis
with
3d
transition-metal
catalysis
has
offered
huge
opportunities
for
modern
synthesis.
This
review
summarizes
the
key
advancements
in
this
direction
published
recent
two
years.
Accounts of Chemical Research,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 19, 2025
ConspectusIn
recent
years,
our
research
group
has
dedicated
significant
effort
to
the
field
of
asymmetric
organometallic
electrochemical
synthesis
(AOES),
which
integrates
electrochemistry
with
transition
metal
catalysis.
On
one
hand,
we
have
rationalized
that
compounds
can
serve
as
molecular
electrocatalysts
(mediators)
reduce
overpotentials
and
enhance
both
reactivity
selectivity
reactions.
other
conditions
for
catalysis
be
substantially
improved
through
electrochemistry,
enabling
precise
modulation
metal's
oxidation
state
by
controlling
potentials
regulating
electron
transfer
rate
via
current
adjustments.
This
synergistic
approach
addresses
key
challenges
inherent
in
traditional
catalysis,
particularly
those
related
use
redox-active
chemical
reagents.
Furthermore,
redox
conveniently
tuned
modifying
their
ligands,
thereby
governing
reaction
regioselectivity
stereoselectivity.
As
a
result,
AOES
emerged
powerful
promising
tool
chiral
compounds.In
this
Account,
summarize
contextualize
efforts
AOES.
Our
primary
strategy
involves
leveraging
controllability
potential
regulate
organometallics,
facilitating
desired
An
efficient
platform
was
established
under
mild
conditions,
significantly
reducing
reliance
on
been
systematically
categorized
into
three
sections
based
distinct
electrolysis
modes:
combined
anodic
oxidation,
cathodic
reduction,
paired
electrolysis.
In
each
section,
highlight
innovative
discoveries
tailored
unique
characteristics
respective
modes.In
many
transformations,
metal-catalyzed
reactions
involving
reagents
utilizing
exhibit
similar
reactivities.
However,
also
observed
notable
differences
certain
cases.
These
findings
include
following:
(1)
Enhanced
efficiency
synthesis:
instance,
Rh-catalyzed
enantioselective
functionalization
C–H
bonds
demonstrates
superior
efficiency.
(2)
Expanded
scope
transformations:
previously
challenging
achieved
due
tunability
potentials.
A
example
is
reductive
coupling
aryl
chlorides,
expands
range
accessible
transformations.
Additionally,
mechanistic
studies
explore
techniques
intrinsic
such
controlled
experiments,
impact
electrode
materials
catalyst
performance,
cyclic
voltammetry
studies.
investigations
provide
more
intuitive
understanding
behavior
catalysts
study
mechanisms,
guide
design
new
catalytic
systems.The
advancements
offer
robust
environmentally
friendly
sustainable
selective
By
integrating
developed
versatile
organic
not
only
enhances
but
reduces
environmental
impact.
We
anticipate
Account
will
stimulate
further
innovation
realm
AOES,
leading
discovery
systems
development
synthetic
methodologies.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(7), P. 4395 - 4406
Published: March 8, 2024
Asymmetric
reductive
three-component
arylalkylation
of
alkenes
via
the
radical
relay
method
has
been
well
established,
while
asymmetric
migratory
insertion
strategy
remains
unexplored.
We
report
enantioselective
nickel-catalyzed
cross-electrophile
with
aryl-
and
alkyl
halides
an
integrated
Heck
carbometalation/radical
cross-coupling
sequence.
This
protocol
employing
a
chiral
Ni/PHOX
catalytic
system
allows
terminal
internal
to
successfully
engage
exquisite
control
regio-,
chemo-,
stereoselectivity.
More
importantly,
this
undergoes
regio-
arylnickelation
followed
by
Csp3–Csp3
elimination,
thus
exhibiting
reverse
regioselectivity
method.
Mild
reaction
conditions
exceptional
functional
group
tolerance
facilitate
method's
compatibility
bioactive
motifs
modular
synthesis
biologically
active
compounds.
The
experiments
density
theory
calculations
provide
insights
into
mechanism
origin
stereoselectivity,
hemilabile
nature
PHOX
ligand
is
critical
for
achieving
arylalkylation.
Accounts of Chemical Research,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 13, 2024
ConspectusIn
recent
years,
radical-mediated
cross-coupling
reactions
have
emerged
as
a
compelling
strategy
for
achieving
rich
diversity
in
molecular
topologies
under
benign
conditions.
However,
the
inherent
high
reactivity
of
radicals
presents
considerable
challenges
controlling
reaction
pathways
and
selectivity,
which
often
results
limited
range
substrates
constrained
profile.
Given
capacity
visible-light
photoredox
catalysis
to
generate
wide
variety
reactive
radical
ions
controlled
manner
propensity
copper
complexes
toward
species,
we
envisaged
that
synergy
between
chiral
catalysts
photoactive
would
pave
way
developing
innovative
strategies.
This
integration
is
poised
unlock
broad
spectrum
enantioselective
multicomponent
reactions.In
this
Account,
describe
our
insights
efforts
realm
reactions.
These
advancements
been
achieved
through
application
dual
photoredox/copper
or
bifunctional
visible
light
irradiation.
Our
work
systematically
divided
into
two
sections
based
on
activation
modes.
The
first
section
focuses
photoinduced
copper-catalyzed
C-C
C-O
bond
formation
addition/nucleophilic
trap
sequence.
discussion
particularly
concentrated
asymmetric
carbocyanation
carboarylation
vinylarenes,
1,3-enynes,
1,3-dienes.
findings
underscore
irradiation
with
can
adeptly
modulate
pace
generation,
thus
orchestrating
consecutive
stages
ensuring
attainment
both
chemo-
stereoselectivity.
In
domain
formation,
leveraging
carboxylic
acids
nucleophilic
oxygen
source,
introduce
suite
esterification
benzylic,
allylic,
propargylic
radicals.
are
derived
from
precursors,
showcasing
versatility
approach.
following
highlights
discovery
field
catalysis,
enables
three-component
transformations
via
direct
aromatic
alkenes.
methodology
begins
generation
formal
distonic
anions
photocatalytic
single-electron
reduction
alkenes,
thus,
enabling
orthogonal
reactivity.
Employing
H
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(24), P. 16892 - 16901
Published: June 6, 2024
The
development
of
a
catalytic
method
for
stereogenic
carbon
center
formation
holds
immense
significance
in
organic
synthesis.
Transition-metal-catalyzed
cross-coupling
reaction
has
been
regarded
as
straightforward
and
efficient
tool
stereoselectively
forging
C–C
bond.
Nevertheless,
the
creation
acyclic
all-carbon
quaternary-containing
vicinal
stereocenters
remains
notoriously
challenging
within
domain
chemistry
despite
their
prominence
various
bioactive
small
molecules.
Herein,
we
describe
palladium-catalyzed
asymmetric
multicomponent
trisubstituted
alkene
with
aryl
diazonium
salts
arylboronic
acids
to
realize
tertiary-quaternary
centers
high
regio-,
distereo-,
enantioselectivity.
Specifically,
precise
manipulation
stereoconfiguration
alkenes
enables
divergent
stereoselective
reaction,
thus
allowing
facile
construction
all
four
enantiomers.
Harnessing
ligand-swap
strategy
involving
chiral
bisoxazoline
an
achiral
fumarate
individually
accelerates
enantioselective
migratory
insertion
reductive
elimination
step
process,
supported
by
density
functional
theory
(DFT)
calculations,
obviating
requirement
neighboring
directing
group
internal
olefin
skeleton.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
16(15)
Published: March 15, 2024
Abstract
Low‐valent
chromium
catalysts
are
cheap
and
less
toxic
compared
to
other
transition
metal
catalysts.
Here
in,
we
reported
a
ligand‐free
chromium(III)‐catalyzed
manganese
reductive
cross‐coupling
of
unactivated
alkyl
electrophiles,
such
as
sulfonates
chlorides,
with
trisulfide
dioxides
thiolation
agents
form
carbon−sulfur
bonds.
The
powerful
method
featured
ample
substrate
scope
wide
functional
group
tolerance,
constructing
large
number
unsymmetrical
disulfides
under
simple
conditions.
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.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(20), P. 15790 - 15798
Published: Oct. 10, 2024
Here,
we
report
a
photoredox
and
nickel-catalyzed
cross-electrophile
coupling
strategy
for
the
asymmetric
three-component
1,2-alkylarylation
of
vinyl
boronates
with
(hetero)aryl
bromides
(2°,
3°)-alkyl
redox-active
esters
in
presence
Hantzsch
ester.
With
fluorinated
pyridyl-substituted
chiral
biimidazoline
ligand,
this
reaction
enables
straightforward
access
to
wide
variety
synthetically
valuable
α-aryl
from
readily
available
starting
materials.
This
features
mild
conditions,
broad
substrate
generality,
good
functional
group
tolerance
proceeds
without
using
metal
reductants
or
alkyl
halides.
Furthermore,
alkenyl
halides
other
electron-deficient
alkenes
such
as
acrylates
phosphonates
can
be
applied
successfully.
Preliminary
mechanistic
studies
shed
light
on
potential
pathways
roles
organic
amines.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Jan. 28, 2025
Abstract
Motivated
by
the
inherent
benefits
of
synergistically
combining
electrochemical
methodologies
with
nickel
catalysis,
we
present
here
a
Ni-catalyzed
enantioselective
electroreductive
cross-coupling
benzyl
chlorides
aryl
halides,
yielding
chiral
1,1-diaryl
compounds
good
to
excellent
enantioselectivity.
This
catalytic
reaction
can
not
only
be
applied
chlorides/bromides,
which
are
challenging
access
other
means,
but
also
containing
silicon
groups.
Additionally,
absence
sacrificial
anode
lays
foundation
for
scalability.
The
combination
cyclic
voltammetry
analysis
electrode
potential
studies
suggests
that
Ni
I
species
activate
halides
via
oxidative
addition
and
alkyl
single
electron
transfer.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 30, 2025
A
Ni/photoredox
dual-catalyzed
multicomponent
cross-electrophile
coupling
of
N-vinyl
amides
with
(hetero)aryl
halides
and
(2°,
3°)-alkyl
redox-active
esters
in
the
presence
cheap
reductant
Hantzsch
ester
is
reported
here.
This
reductive
protocol
provides
direct
access
to
various
synthetically
challenging
chiral
α-arylamides
good
yields
excellent
enantioselectivities
(up
99%
ee,
majority
exceeding
97%
ee),
which
can
be
further
derived
into
primary
secondary
amines.
Preliminary
experimental
studies
shed
light
on
potential
catalytic
pathways.
The Chemical Record,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 3, 2025
Abstract
Owing
to
their
wide
utilizations
in
synthesis
and
products
prevalence
numerous
natural
products,
pharmaceuticals
functional
materials,
the
alkene
difunctionalization
methods
for
selective
transformations
of
olefins
are
important
have
attracted
much
attention
form
synthetic
chemists.
Among
them,
electrochemical
reaction
is
particularly
promising
has
becoming
a
potent
sustainable
tool
alkenes
into
vicinal
difunctionalized
structures
organic
through
simultaneous
incorporation
two
groups.
Herein,
we
summarize
recent
progress
reactions
according
types
as
well
category
radicals
over
past
five
years.
By
selecting
remarkable
examples,
elaborately
discussed
substrate
scope
mechanisms
olefin
reaction.