Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(62)
Published: Aug. 10, 2024
The
difunctionalization
of
alkenes
represents
a
powerful
tool
to
incorporate
two
functional
groups
into
the
alkene
bones
for
increasing
molecular
complexity
and
has
been
widely
utilizations
in
chemical
synthesis.
Upon
catalysis
green,
sustainable,
mild
photo-/electrochemistry
technologies,
much
attentions
have
attracted
development
new
tactics
transformations
important
alkane
feedstocks
driven
by
C-H
radical
functionalization.
Herein,
we
summarize
recent
advances
photo-/electrocatalytic
enabled
We
detailedly
discuss
substrate
scope
mechanisms
reactions
selecting
impressive
synthetic
examples,
which
are
divided
four
sections
based
on
final
terminated
step,
including
oxidative
radical-polar
crossover
coupling,
reductive
radical-radical
transition-metal-catalyzed
coupling.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(2), P. 1522 - 1531
Published: Jan. 3, 2024
The
development
of
a
reliable
strategy
for
stereodivergent
radical
reactions
that
allows
convenient
access
to
all
stereoisomers
homocoupling
adducts
with
multiple
stereogenic
centers
remains
an
unmet
goal
in
organic
synthesis.
Herein,
we
describe
dual-catalyzed
electrooxidative
C(sp3)–H/C(sp3)–H
complete
absolute
and
relative
stereocontrol
the
synthesis
molecules
contiguous
quaternary
stereocenters
general
predictable
manner.
reaction
is
achieved
by
synergistically
utilizing
two
distinct
chiral
catalysts
convert
identical
racemic
substrates
into
inherently
distinctive
reactive
intermediates,
dictate
enantioselective
addition,
allow
full
complement
stereoisomeric
products
via
simple
catalyst
permutation.
successful
execution
dual-electrocatalytic
programmed
activation
provides
significant
conceptual
advantage
will
serve
as
useful
foundation
further
research
cooperative
stereocontrolled
transformations
diversity-oriented
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(16), P. 1913 - 1928
Published: April 24, 2024
Comprehensive
Summary
Organic
fluorine
compounds
are
ubiquitous
and
pivotally
important
organic
molecules,
yet
their
activation
transformation
have
long
been
a
formidable
challenge
due
to
the
high
energy
low
reactivity
of
C—F
bonds.
electrosynthesis,
an
environmentally
benign
synthetic
method
in
chemistry,
enables
myriad
chemical
transformations
without
need
for
external
redox
reagents.
In
recent
years,
electrochemistry
has
emerged
as
powerful
tool
achieving
bonds
fluorine‐containing
compounds.
This
review
aims
succinctly
recapitulate
latest
advancements
electrochemical
defluorinative
delve
into
reaction
design,
mechanistic
insights,
developmental
prospects
these
methods.
Key
Scientists
1959,
Lund
was
first
pioneer
electroreduction
CF
3
CH
group.
Electrochemistry
lately
provided
new
opportunities
efficient
conversion
fluorides.
2020,
Zhou
coworkers
discovered
carboxylation
α‐CF
alkenes.
Lambert
colleagues
reported
electrophotocatalytic
amination
aryl
Electrochemical
hydrodefluorination
trifluoromethylketones
developed
by
Lennox
2021.
same
year,
Wang
Guo
disclosed
radical
alkylation
alkenes
with
Katritzky
salts
alkyl
precursors.
Subsequently,
Wu
Liao
described
transition‐metal‐free,
site‐selective
arylation
polyfluoroarenes
(het)arenes
using
paired
electrophotocatalysis.
2023,
numerous
efforts
were
made
achieve
bond
activation.
Xia
organoboron‐controlled
chemoselective
sequential
(deutero)hydrodefluorination
trifluoroacetamides.
Accounts of Chemical Research,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 13, 2025
ConspectusMolecular
photoelectrocatalysis,
which
combines
the
merits
of
photocatalysis
and
organic
electrosynthesis,
including
their
green
attributes
capacity
to
offer
novel
reactivity
selectivity,
represents
an
emerging
field
in
chemistry
that
addresses
growing
demands
for
environmental
sustainability
synthetic
efficiency.
This
synergistic
approach
permits
access
a
wider
range
redox
potentials,
facilitates
transformations
under
gentler
electrode
decreases
use
external
harsh
reagents.
Despite
these
potential
advantages,
this
area
did
not
receive
significant
attention
until
2019,
when
we
others
reported
first
examples
modern
molecular
photoelectrocatalysis.
These
studies
showcased
immense
hybrid
strategy,
only
inherits
strengths
its
parent
fields
but
also
unlocks
unprecedented
enabling
challenging
mild
conditions
while
minimizing
reliance
on
stoichiometric
oxidants
or
reductants.In
Account,
present
our
efforts
develop
photoelectrocatalytic
strategies
leverage
homogeneous
catalysts
facilitate
diverse
radical
reactions.
By
integrating
electrocatalysis
with
key
photoinduced
processes
such
as
single
electron
transfer
(SET),
ligand-to-metal
charge
(LMCT),
hydrogen
atom
(HAT),
have
established
methods
transform
substrates
organotrifluoroborates,
arenes,
carboxylic
acids,
alkanes
into
reactive
intermediates.
intermediates
subsequently
engage
heteroarene
C-H
functionalization
Importantly,
photoelectrochemical
catalysts,
generated
bulk
solution
readily
participate
efficient
reactions
without
undergoing
further
overoxidation
carbocations,
common
challenge
conventional
electrochemical
systems.By
integration
photoelectrocatalysis
asymmetric
catalysis,
developed
catalysis
(PEAC),
proves
be
enantioselective
synthesis
chiral
nitriles.
involves
two
relay
catalytic
cycles:
initial
process
engenders
benzylic
radicals
from
precursors
alkyl
aryl
alkenes,
C-radicals
are
then
subjected
cyanation
subsequent
copper-electrocatalytic
cycle.Within
realm
oxidative
transformations,
anode
serves
crucial
component
recycling
generating
photocatalyst,
cathode
promotes
proton
reduction.
dual
functionality
enables
via
H
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(7), P. 4199 - 4208
Published: Jan. 1, 2024
A
new
photoelectrocatalytic
mode
permits
the
synthesis
of
polycyclic
pyrimidin-4-ones
through
dehydrogenative
cyclization
malonates
with
unactivated
alkenes.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(18), P. 5278 - 5305
Published: Jan. 1, 2024
This
review
summarizes
the
latest
methodological
advances
in
photocatalytic
C(sp
3
)–H
functionalization,
with
a
particular
emphasis
on
formation
of
C–P,
C–B,
C–S
bonds,
etc
.,
and
some
prominent
efforts
asymmetric
C–H
functionalization.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(14), P. 4024 - 4040
Published: Jan. 1, 2024
This
review
provides
a
comprehensive
overview
of
metal
catalysis
in
photo-electrochemical
systems,
discussing
reaction
mechanisms
and
offering
prospects
for
this
triadic
catalytic
mode.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(14), P. 8315 - 8322
Published: Jan. 1, 2024
A
photoelectrochemical
approach
for
the
carboacylation/silanoylation
of
alkenes
with
alkanes/hydrosilanes
is
described.
The
method
offers
a
new
perspective
chemists
to
rapidly
obtain
various
ketones
high
levels
structural
complexity.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(10), P. 2352 - 2362
Published: April 5, 2024
Abstract
While
the
emergence
of
electrophotochemistry
provides
opportunities,
such
a
chemistry
at
this
stage
suffers
from
limited
reaction
types
and
high
photocatalyst
loadings.
A
self‐catalyzed
electrophotosynthesis
as
well
one
with
low
loading
is
presented.
These
external‐oxidant‐free
cyclizations
are
enabling
applicable
to
range
activated
alkenes,
affording
diverse
array
thiocyanato
heterocycles
including
4‐pyrrolin‐2‐ones,
isoquinoline‐1,3‐diones,
indolo[2,1‐
]isoquinolin‐6(5
H
)‐ones,
benzoimidazo[2,1‐
)‐ones
indolin‐2‐ones,
protocols
amenable
late‐stage
diversification
complex
molecular
architectures
gram‐scale
syntheses.
Sunlight
could
serve
light
source,
be
conducted
in
an
all‐solar‐driven
mode
using
commercially
available
photovoltaic
panel
produce
electricity.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(13), P. 9648 - 9654
Published: June 12, 2024
A
mild
carboamidation
of
electronically
different
styrenes
with
diverse
hydrocarbons
was
developed
by
merging
photocatalysis
and
electrochemistry
without
using
external
oxidants.
The
reaction
proceeds
through
a
tandem
photocatalytic
hydrogen
atom
transfer
(HAT),
radical
addition
to
styrenes,
polar
crossover,
subsequent
Ritter-type
amidation.
Key
engaging
unactivated
alkanes
is
the
use
tetrabutylammonium
decatungstate
(TBADT)
as
HAT
photocatalyst,
which
regenerated
from
its
reduced
form
anodic
oxidation.
set
C–H
precursors,
including
alkanes,
successfully
utilized.
Styrenes
bearing
functionalities
in
their
arene
rings
were
selectively
difunctionalized.
Overall,
we
demonstrate
how
photoelectrochemistry
forges
unconventional
reactivity
an
oxidative
crossover.
