Abstract
Despite
the
rich
photochemistry
of
3d‐metal
complexes,
utilization
excited‐state
reactivity
these
compounds
in
organic
synthesis
has
been
historically
overlooked.
The
advent
photoredox
catalysis
changed
perception
synthetic
chemists
towards
photochemistry,
and
nowadays
potential
photoinduced,
outer‐sphere
single‐electron
transfer
events
is
widely
recognized.
More
recently,
an
emerging
new
mode
photoactivation
taken
spotlight,
based
on
inner‐sphere
triggered
by
population
ligand‐to‐metal
charge‐transfer
(LMCT)
excited
states.
Contrarily
to
photoredox,
LMCT‐activation
does
not
rely
matching
redox
potentials,
offers
unique
profiles
particularly
well
suited
Earth‐abundant
metal
complexes.
Those
appealing
features
are
propelling
development
methods
using
this
blueprint
generate
highly
reactive
open‐shell
species
under
mild
conditions.
aim
contribution
provide
a
didactical
tool
for
comprehension
concept
facilitate
methodologies
achieve
sustainable
chemical
transformations.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(17), С. 9369 - 9388
Опубликована: Апрель 20, 2023
Photoredox
catalysis
of
organic
reactions
driven
by
iron
has
attracted
substantial
attention
throughout
recent
years,
due
to
potential
environmental
and
economic
benefits.
In
this
Perspective,
three
major
strategies
were
identified
that
have
been
employed
date
achieve
reactivities
comparable
the
successful
noble
metal
photoredox
catalysis:
(1)
Direct
replacement
a
center
in
archetypal
polypyridyl
complexes,
resulting
metal-centered
photofunctional
state.
(2)
situ
generation
photoactive
complexes
substrate
coordination
where
are
via
intramolecular
electron
transfer
involving
charge-transfer
states,
for
example,
through
visible-light-induced
homolysis.
(3)
Improving
excited-state
lifetimes
redox
potentials
states
new
ligand
design.
We
seek
give
an
overview
evaluation
developments
rapidly
growing
field
and,
at
same
time,
provide
outlook
on
future
iron-based
catalysis.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(30), С. 13895 - 13902
Опубликована: Июль 21, 2022
Selective
cleavage
and
functionalization
of
C–C
bonds
in
alcohols
is
gaining
increasing
interest
organic
synthesis
biomass
conversion.
In
particular,
the
development
redox-neutral
catalytic
methods
with
cheap
catalysts
clean
energy
utmost
interest.
this
work,
we
report
a
versatile
method
for
ring-opening
cycloalkanols
by
electrophotochemical
(EPC)
cerium
(Ce)
catalysis.
The
EPC-Ce-enabled
catalysis
allows
different
ring
sizes
to
be
cleaved
while
tolerating
broad
range
functional
groups.
Notably,
presence
chloride
as
counteranion
electrolyte,
protocol
selectively
leads
formation
C–CN,
C–C,
C–S,
or
C–oxime
instead
C–halide
bond
after
β-scission.
A
preliminary
mechanistic
investigation
indicates
that
redox-active
Ce
catalyst
can
tuned
electro-oxidation
photo-reduction,
thus
avoiding
use
an
external
oxidant.
Spectroscopic
characterizations
(cyclic
voltammetry,
UV–vis,
electron
paramagnetic
resonance,
X-ray
absorption
fine
structure)
suggest
Ce(III)/Ce(IV)
pathway
transformation,
which
Ce(IV)-alkoxide
involved.
ACS Catalysis,
Год журнала:
2023,
Номер
13(3), С. 1678 - 1685
Опубликована: Янв. 13, 2023
We
report
a
photoinduced
iron/copper
dual-catalytic
strategy
for
the
radical
decarboxylation
functionalization
of
aliphatic
carboxylic
acids.
The
ligand-to-iron
charge
transfer
process
under
light
was
initially
occurred
to
generate
an
unstabilized
alkyl
radical,
and
copper
catalyst
delivered
enabled
subsequent
coupling
reactions
form
C–N
or
C–C
bonds.
By
merging
iron-catalyzed
with
catalysis,
this
system
allows
smooth
conversion
wide
range
acids
amination,
decarboxylative
dehydrogenation,
alkylation
efficiently.
A
variety
complex
drug
natural
molecules
is
applicable,
suggesting
that
would
facilitate
rapid
compound
library
synthesis
benefit
discovery
pharmaceutical
agents.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 6, 2025
The
integration
of
ligand-to-metal
charge
transfer
(LMCT)
catalytic
paradigms
with
radical
intermediates
has
transformed
the
selective
functionalization
inert
C-H
bonds,
facilitating
use
nonprecious
metal
catalysts
in
demanding
transformations.
Notably,
aerobic
carbonylation
methane
to
acetic
acid
remains
formidable
due
rapid
oxidation
methyl
radicals,
producing
undesired
C1
oxygenates.
We
present
an
iron
terpyridine
catalyst
utilizing
LMCT
achieve
exceptional
C2/C1
selectivity
through
synergistic
photoexcitation,
generation,
and
carbonylation.
Mechanistic
studies
highlight
critical
roles
Fe(II)
Fe-carbonyl
complexes
bypassing
via
a
rebound-like
pathway,
unlocking
unprecedented
efficiency
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 4665 - 4680
Опубликована: Март 5, 2025
Transition
metal
catalysis
is
an
indispensable
tool
for
organic
synthesis
that
has
been
harnessed,
modulated,
and
perfected
many
decades
by
careful
selection
of
centers
ligands,
giving
rise
to
synthetic
methods
with
unparalleled
efficiency
chemoselectivity.
Recent
developments
have
demonstrated
how
light
irradiation
can
also
be
recruited
as
a
powerful
dramatically
alter
the
outcome
catalytic
reactions,
providing
access
innovative
pathways
remarkable
potential.
In
this
context,
adoption
photochemical
conditions
mainstream
strategy
drive
reactions
unveiled
exciting
opportunities
exploit
rich
excited-state
framework
transition
metals
applications.
This
Perspective
examines
advances
in
application
complexes
standalone
photocatalysts,
exploiting
innate
reactivity
their
excited
states
beyond
common
use
photoredox
catalysts.
An
account
relevant
examples
dissected
provide
discussion
on
electronic
reorganization,
orbitals
involved,
associated
different
types
states.
analysis
aims
practitioners
fundamental
principles
guiding
strategies
understand,
design,
apply
light-activation
homogeneous
synthesis.
Organic Letters,
Год журнала:
2022,
Номер
24(32), С. 5972 - 5976
Опубликована: Авг. 11, 2022
An
efficient
and
inexpensive
protocol
for
the
direct
decarboxylative
fluorination
of
aliphatic
carboxylic
acids
catalyzed
with
iron
salts
under
visible
light
is
presented.
This
new
method
allows
facile
a
diverse
array
even
on
gram
scale
using
Schlenk
flask
without
loss
efficiency.
Mechanistic
studies
suggest
that
photoinduced
ligand-to-metal
charge
transfer
process
enables
generation
key
step
to
generate
carboxyl
radical
intermediates.
Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
364(24), С. 4189 - 4230
Опубликована: Дек. 3, 2022
Abstract
In
the
quest
for
sustainable
processes,
selection
of
resources
and
catalysts
is
central
importance.
Carboxylic
acids,
which
are
abundant,
stable
ideally
biobased
feedstocks,
can
be
considered
as
attractive
platforms
towards
a
range
functionalized
molecules.
A
recent
resurgence
photoinduced
ligand‐to‐metal
charge
transfer
(LMCT)
carboxylates
led
to
tremendous
developments
in
field
earth‐abundant
metal
mediated,
visible‐light
induced
(non)‐decarboxylative
transformations
carboxylic
acids.
These
reactions
combine
use
available
starting
materials,
low‐consuming
energy
source
abundant
catalysts.
Besides
these
undeniable
advantages,
they
also
provide
mild,
highly
selective
innovative
conditions
complex
molecule
functionalization.
The
objective
this
review
give
an
overview
advances
LMCT
with
special
focus
on
mechanistic
aspects
transformations.
magnified
image
Chemical Science,
Год журнала:
2022,
Номер
13(45), С. 13611 - 13616
Опубликована: Янв. 1, 2022
Sulfoximines
are
synthetically
important
scaffolds
and
serve
roles
in
drug
discovery.
Currently,
there
is
no
solution
to
decarboxylative
sulfoximination
of
benzoic
acids;
although
thoroughly
investigated,
limited
substrate
scope
harsh
reaction
conditions
still
hold
back
traditional
thermal
aromatic
functionalization.
Herein,
we
realize
the
first
acids
via
photo-induced
ligand
copper
charge
transfer
(copper-LMCT)-enabled
carbometalation.
The
transformation
proceeds
under
mild
conditions,
has
a
broad
scope,
can
be
applied
late-stage
functionalization
complex
small
molecules.
