Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(43), С. 29450 - 29461
Опубликована: Окт. 17, 2024
The
direct
coupling
of
alkene
feedstocks
with
aldehydes
represents
an
expedient
approach
to
the
generation
new
and
structurally
diverse
C(sp3)-hybridized
alcohols
that
are
primed
for
elaboration
into
privileged
architectures.
Despite
their
abundance,
current
disconnection
strategies
enabling
carbon–carbon
π-bonds
remain
challenging
because
contemporary
methods
often
limited
by
substrate
or
functional
group
tolerance
compatibility
in
complex
molecular
environments.
Here,
we
report
a
between
simple
alkenes,
heteroarenes
unactivated
aliphatic
via
electrochemically
induced
reductive
activation
C–C
π-bonds.
cornerstone
this
is
discovery
rapid
alternating
polarity
(rAP)
electrolysis
access
highly
reactive
radical
anion
intermediates
derived
from
conjugated
alkenes
heterocyclic
compounds.
Our
developed
catalyst-free
protocol
enables
alcohol
products.
This
achieved
controlled
reduction
C2–C3
π-bond
unprecedented
dearomative
functionalization
Experimental
mechanistic
studies
demonstrate
kinetically
biased
single-electron
over
aldehydes.
Application
rAP
chemoselective
olefinic
avoids
undesired
saturative
overreduction.
Overall,
technology
provides
versatile
olefin
heterocycle
aldehydes,
offering
straightforward
C(sp3)-rich
oxygenated
scaffolds.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(12), С. 6600 - 6624
Опубликована: Янв. 1, 2024
Dearomatization
has
emerged
as
a
powerful
tool
for
rapid
construction
of
3D
molecular
architectures
from
simple,
abundant,
and
planar
(hetero)arenes.
The
field
evolved
beyond
simple
dearomatization
driven
by
new
synthetic
technology
development.
With
the
renaissance
photocatalysis
expansion
activation
mode,
last
few
years
have
witnessed
impressive
developments
in
innovative
photochemical
methodologies,
enabling
skeletal
modifications
dearomatized
structures.
They
offer
truly
efficient
useful
tools
facile
highly
complex
structures,
which
are
viable
natural
product
synthesis
drug
discovery.
In
this
review,
we
aim
to
provide
mechanistically
insightful
overview
on
these
innovations
based
degree
alteration,
categorized
into
dearomative
functionalization
editing,
highlight
their
utilities.
Chemical Reviews,
Год журнала:
2024,
Номер
124(21), С. 12264 - 12304
Опубликована: Окт. 23, 2024
Electrocatalysis
and
photocatalysis
have
been
the
focus
of
extensive
research
efforts
in
organic
synthesis
recent
decades,
these
powerful
strategies
provided
a
wealth
new
methods
to
construct
complex
molecules.
Despite
intense
efforts,
only
recently
has
there
significant
on
combined
use
two
modalities.
Nevertheless,
past
five
years
witnessed
rapidly
growing
interest
area
electrophotocatalysis.
This
hybrid
strategy
capitalizes
enormous
benefits
using
photons
as
reagents
while
also
employing
an
electric
potential
convenient
tunable
source
or
sink
electrons.
Research
this
topic
led
number
for
C-H
functionalization,
reductive
cross-coupling,
olefin
addition
among
others.
field
seen
broad
range
catalyst
types,
including
both
metal
organocatalysts.
Of
particular
note
work
with
open-shell
photocatalysts,
which
tend
comparatively
large
redox
potentials.
Electrochemistry
provides
means
generate
such
species,
making
electrophotocatalysis
particularly
amenable
intriguing
class
catalyst.
review
surveys
applied
synthesis,
organized
broadly
into
oxidative,
reductive,
neutral
transformations.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(10), С. 2352 - 2362
Опубликована: Апрель 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,
Год журнала:
2024,
Номер
14(13), С. 9648 - 9654
Опубликована: Июнь 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.
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.
Abstract
This
review
delves
into
the
innovative
field
of
interfacial
photoelectrochemical
(iPEC)
and
(PEC)
catalysis,
dynamic
synthesis
methodologies
that
seamlessly
integrates
electrochemical
photoredox
catalysis
for
efficient
environmentally
friendly
reactions.
Utilizing
minute
quantities
photocatalysts,
visible
light
becomes
a
powerful
tool,
generating
transient
excited
states
to
catalyze
spectrum
reactions
through
single‐electron
oxidation
or
reduction
events.
The
categorizes
recent
advancements,
highlighting
applications
in
organic
synthesis,
late‐stage
modifications,
distinctive
features
methodology.
Despite
being
its
early
stages,
this
synergistic
approach
holds
great
promise
propelling
forward,
with
potential
large‐scale
diverse
functionalizations,
including
asymmetric
bioconjugation
strategies
biomolecule
modifications.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(36)
Опубликована: Апрель 23, 2024
Three
hybrid
electrochemical
protocols,
which
involve
the
energy
transfer,
direct
photolysis
and
N-hydroxyphthalimide
catalyst,
respectively,
are
presented
for
selenylation/cyclization
of
fragile
substrates
3-aza-1,5-dienes
with
diorganyl
diselenides
to
afford
3-selenomethyl-4-pyrrolin-2-ones.
The
two
electrophotocatalytic
reactions
indirect
electrolysis
one
both
regioselective
external-oxidant-
transition-metal-free,
associated
a
broad
substrate
scope
high
Se-economy,
all
three
methods
amenable
gram-scale
syntheses,
late-stage
functionalizations,
sunlight-induced
experiments
all-solar-driven
syntheses.
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 5269 - 5274
Опубликована: Март 25, 2024
Enabling
reactions
of
traditional
substrates
that
are
inert
to
Pd
catalysts
has
the
potential
for
further
advancements
in
field
chemistry.
In
this
study,
we
developed
a
method
generating
ketyl
radicals
through
reaction
photoexcited
species
with
ketones.
Upon
subsequent
olefins,
generated
yielded
Pd-specific
reductive
and
Heck-type
coupling
products.
Mechanistic
studies
indicated
proposed
radical
generation
exhibits
characteristics
distinct
from
those
methods
such
as
SmI2
reduction
photoredox-catalyzed
reactions.
