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.
Chemical Reviews,
Год журнала:
2023,
Номер
123(8), С. 4237 - 4352
Опубликована: Янв. 24, 2023
The
emergence
of
modern
photocatalysis,
characterized
by
mildness
and
selectivity,
has
significantly
spurred
innovative
late-stage
C–H
functionalization
approaches
that
make
use
low
energy
photons
as
a
controllable
source.
Compared
to
traditional
strategies,
photocatalysis
paves
the
way
toward
complementary
and/or
previously
unattainable
regio-
chemoselectivities.
Merging
compelling
benefits
with
workflow
offers
potentially
unmatched
arsenal
tackle
drug
development
campaigns
beyond.
This
Review
highlights
photocatalytic
strategies
small-molecule
drugs,
agrochemicals,
natural
products,
classified
according
targeted
bond
newly
formed
one.
Emphasis
is
devoted
identifying,
describing,
comparing
main
mechanistic
scenarios.
draws
critical
comparison
between
established
ionic
chemistry
photocatalyzed
radical-based
manifolds.
aims
establish
current
state-of-the-art
illustrate
key
unsolved
challenges
be
addressed
in
future.
authors
aim
introduce
general
readership
functionalization,
specialist
practitioners
evaluation
methodologies,
potential
for
improvement,
future
uncharted
directions.
Chemical Reviews,
Год журнала:
2023,
Номер
123(9), С. 5225 - 5261
Опубликована: Янв. 20, 2023
Because
sunlight
is
the
most
abundant
energy
source
on
earth,
it
has
huge
potential
for
practical
applications
ranging
from
sustainable
supply
to
light
driven
chemistry.
From
a
chemical
perspective,
excited
states
generated
by
make
thermodynamically
uphill
reactions
possible,
which
forms
basis
storage
into
fuels.
In
addition,
with
light,
open-shell
species
can
be
open
up
new
reaction
pathways
in
organic
synthesis.
Crucial
are
photosensitizers,
absorb
and
transfer
substrates
various
mechanisms,
processes
that
highly
depend
distance
between
molecules
involved.
Supramolecular
coordination
cages
well
studied
synthetically
accessible
vessels
single
cavities
guest
binding,
ensuring
close
proximity
of
different
components.
Due
high
modularity
their
size,
shape,
nature
metal
centers
ligands,
ideal
platforms
exploit
preorganization
photocatalysis.
Herein
we
focus
application
supramolecular
photocatalysis
artificial
photosynthesis
photo(redox)
catalysis.
Finally,
brief
overview
immobilization
strategies
provides
tools
implementing
devices.
This
review
inspiration
future
design
photocatalytic
host-guest
systems
producing
solar
fuels
complex
molecules.
Science,
Год журнала:
2023,
Номер
381(6653), С. 75 - 81
Опубликована: Июль 6, 2023
Skeletal
ring
enlargement
is
gaining
renewed
interest
in
synthetic
chemistry
and
has
recently
focused
on
insertion
of
one
or
two
atoms.
Strategies
for
heterocyclic
expansion
through
small-ring
remain
elusive,
although
they
would
lead
to
the
efficient
formation
bicyclic
products.
Here,
we
report
a
photoinduced
dearomative
thiophenes
by
bicyclo[1.1.0]butanes
produce
eight-membered
rings
under
mild
conditions.
The
value,
broad
functional-group
compatibility,
excellent
chemo-
regioselectivity
were
demonstrated
scope
evaluation
product
derivatization.
Experimental
computational
studies
point
toward
photoredox-induced
radical
pathway.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(31), С. 14288 - 14296
Опубликована: Июль 27, 2022
The
application
of
abundant
and
inexpensive
fluorine
feedstock
sources
to
synthesize
fluorinated
compounds
is
an
appealing
yet
underexplored
strategy.
Here,
we
report
a
photocatalytic
radical
hydrodifluoromethylation
unactivated
alkenes
with
industrial
chemical,
chlorodifluoromethane
(ClCF2H,
Freon-22).
This
protocol
realized
by
merging
tertiary
amine-ligated
boryl
radical-induced
halogen
atom
transfer
(XAT)
organophotoredox
catalysis
under
blue
light
irradiation.
A
broad
scope
readily
accessible
featuring
variety
functional
groups
drug
natural
product
moieties
could
be
selectively
difluoromethylated
good
efficiency
in
metal-free
manner.
Combined
experimental
computational
studies
suggest
that
the
key
XAT
process
ClCF2H
both
thermodynamically
kinetically
favored
over
hydrogen
pathway
owing
formation
strong
boron–chlorine
(B–Cl)
bond
low-lying
antibonding
orbital
carbon–chlorine
(C–Cl)
bond.
Science,
Год журнала:
2022,
Номер
377(6612), С. 1323 - 1328
Опубликована: Сен. 15, 2022
The
generation
of
carbon
radicals
by
halogen-atom
and
group
transfer
reactions
is
generally
achieved
using
tin
silicon
reagents
that
maximize
the
interplay
enthalpic
(thermodynamic)
polar
(kinetic)
effects.
In
this
work,
we
demonstrate
a
distinct
reactivity
mode
enabled
quantum
mechanical
tunneling
uses
cyclohexadiene
derivative
γ-terpinene
as
abstractor
under
mild
photochemical
conditions.
This
protocol
activates
alkyl
aryl
halides
well
several
alcohol
thiol
derivatives.
Experimental
computational
studies
unveiled
noncanonical
pathway
whereby
cyclohexadienyl
radical
undergoes
concerted
aromatization
or
abstraction
through
an
effective
H
atom.
activation
mechanism
seemingly
thermodynamically
kinetically
unfavorable
but
rendered
feasible
tunneling.
Science,
Год журнала:
2022,
Номер
378(6621), С. 779 - 785
Опубликована: Ноя. 17, 2022
Carbon-hydrogen
(C−H)
functionalization
of
pyridines
is
a
powerful
tool
for
the
rapid
construction
and
derivatization
many
agrochemicals,
pharmaceuticals,
materials.
Because
inherent
electronic
properties
pyridines,
selective
meta
-C−H
challenging.
Here,
we
present
protocol
highly
regioselective
trifluoromethylation,
perfluoroalkylation,
chlorination,
bromination,
iodination,
nitration,
sulfanylation,
selenylation
through
redox-neutral
dearomatization-rearomatization
process.
The
introduced
dearomative
activation
mode
provides
diversification
platform
meta-selective
reactions
on
other
azaarenes
radical
as
well
ionic
pathways.
broad
scope
high
selectivity
these
catalyst-free
render
processes
applicable
late-stage
drugs.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(4), С. 1899 - 1909
Опубликована: Янв. 18, 2022
The
formation
of
carbon-carbon
bonds
lies
at
the
heart
synthetic
organic
chemistry
and
is
widely
applied
to
construct
complex
drugs,
polymers,
materials.
Despite
its
importance,
catalytic
carbonyl
arylation
remains
comparatively
underdeveloped,
due
limited
scope
functional
group
tolerance.
Herein
we
disclose
an
umpolung
strategy
achieve
radical
via
dual
catalysis.
This
redox-neutral
approach
provides
a
complementary
method
Grignard-type
products
from
(hetero)aryl
bromides
aliphatic
aldehydes,
without
need
for
pre-functionalization.
A
sequential
activation,
hydrogen-atom
transfer,
halogen
atom
transfer
process
could
directly
convert
aldehydes
corresponding
ketyl-type
radicals,
which
further
react
with
aryl-nickel
intermediates
in
overall
polarity-reversal
process.
tolerates─among
others─acidic
groups,
heteroaryl
motifs,
sterically
hindered
substrates
has
been
late-stage
modification
drugs
natural
products.
