ACS Catalysis,
Год журнала:
2021,
Номер
11(24), С. 15004 - 15012
Опубликована: Дек. 1, 2021
A
photoredox
activation
mode
of
formate
salts
for
carboxylation
was
developed.
Using
a
salt
as
the
reductant,
carbonyl
source,
and
hydrogen
atom
transfer
reagent,
wide
range
alkenes
can
be
converted
into
acid
products
via
carboxyl
group
strategy
in
an
additive-free
fashion.
Mechanistic
studies
revealed
that
radical
anion
species
(CO2•–
carbon
anions
derived
from
reduction
alkenes)
are
key
intermediates
transformation.
This
method
has
advantages
high
catalytic
efficiency
simple
system,
which
may
allow
this
approach
to
become
promising
industrial
applications.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(14)
Опубликована: Фев. 9, 2024
Abstract
A
visible‐light‐induced,
three‐component
palladium‐catalyzed
1,4‐aminoarylation
of
butadienes
with
readily
available
aryl
halides
and
aliphatic
amines
has
been
developed,
affording
allylamines
excellent
E
‐selectivity.
The
reaction
exhibits
exceptional
control
over
chemo‐,
regio‐,
stereoselectivity,
a
broad
substrate
scope,
high
functional
group
compatibility,
as
demonstrated
by
the
late‐stage
functionalization
bioactive
molecules.
Mechanistic
investigations
are
consistent
photoinduced
radical
Pd(0)‐Pd(I)‐Pd(II)‐Pd(0)
Heck‐Tsuji–Trost
allylation
cascade.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Янв. 22, 2024
Abstract
The
open-shell
catalytically
active
species,
like
radical
cations
or
anions,
generated
by
one-electron
transfer
of
precatalysts
are
widely
used
in
energy-consuming
redox
reactions,
but
their
excited-state
lifetimes
usually
short.
Here,
a
closed-shell
thioxanthone-hydrogen
anion
species
(
3
),
which
can
be
photochemically
converted
to
potent
and
long-lived
reductant,
is
under
electrochemical
conditions,
enabling
the
electrophotocatalytic
hydrogenation.
Notably,
TfOH
regulate
potential
this
system.
In
presence
TfOH,
precatalyst
1
)
reduction
occur
at
low
potential,
so
that
competitive
H
2
evolution
inhibited,
thus
effectively
promoting
hydrogenation
imines.
absence
reducing
ability
system
reach
potency
even
comparable
Na
0
Li
,
thereby
allowing
hydrogenation,
borylation,
stannylation
(hetero)arylation
aryl
halides
construct
C−H,
C−B,
C−Sn,
C−C
bonds.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Фев. 16, 2024
Abstract
Photoexcitation
of
the
electron-donor-acceptor
complexes
have
been
an
effective
approach
to
achieve
radicals
by
triggering
electron
transfer.
However,
catalytic
version
complex
photoactivation
is
quite
underdeveloped
comparing
well-established
utilization
electronically
biased
partners.
In
this
work,
we
utilize
4-nitrophthalonitrile
as
acceptor
facilitate
efficient
π-stacking
with
electron-rich
aromatics
form
complex.
The
characterization
and
energy
profiles
on
cocrystal
1,3,5-trimethoxybenzene
disclose
that
transfer
highly
favorable
under
light
irradiation.
This
catalyst
can
be
efficiently
applied
in
benzylic
C−H
bond
developing
Giese
reaction
alkylanisoles
oxidation
benzyl
alcohols.
A
broad
scope
tolerated
a
mechanism
also
proposed.
Moreover,
corresponding
π-anion
interaction
potassium
formate
further
hydrocarboxylation
alkenes
efficiently.
JACS Au,
Год журнала:
2025,
Номер
5(2), С. 426 - 447
Опубликована: Янв. 29, 2025
Many
important
synthetic-oriented
works
have
proposed
excited
organic
radicals
as
photoactive
species,
yet
mechanistic
studies
raised
doubts
about
whether
they
can
truly
function
photocatalysts.
This
skepticism
originates
from
the
formation
of
(photo)redox-active
degradation
products
and
picosecond
decay
electronically
radicals,
which
is
considered
too
short
for
diffusion-based
photoinduced
electron
transfer
reactions.
From
this
perspective,
we
analyze
synthetic
transformations
where
been
photocatalysts,
comparing
their
theoretical
maximum
state
potentials
with
required
observed
photocatalytic
reactivity.
We
summarize
structurally
similar
photocatalysts
indicating
different
reaction
pathways
some
catalytic
systems,
addressing
cases
radical
exceed
Additionally,
perform
a
kinetic
analysis
to
explain
in
on
subpicosecond
time
scales.
further
rationalize
potential
anti-Kasha
reactivity
higher
states
femtosecond
lifetimes,
highlighting
how
future
photocatalysis
advancements
could
unlock
new
photochemical
pathways.
ACS Catalysis,
Год журнала:
2021,
Номер
11(24), С. 15004 - 15012
Опубликована: Дек. 1, 2021
A
photoredox
activation
mode
of
formate
salts
for
carboxylation
was
developed.
Using
a
salt
as
the
reductant,
carbonyl
source,
and
hydrogen
atom
transfer
reagent,
wide
range
alkenes
can
be
converted
into
acid
products
via
carboxyl
group
strategy
in
an
additive-free
fashion.
Mechanistic
studies
revealed
that
radical
anion
species
(CO2•–
carbon
anions
derived
from
reduction
alkenes)
are
key
intermediates
transformation.
This
method
has
advantages
high
catalytic
efficiency
simple
system,
which
may
allow
this
approach
to
become
promising
industrial
applications.
