ACS Sustainable Chemistry & Engineering,
Journal Year:
2022,
Volume and Issue:
10(30), P. 9665 - 9678
Published: July 21, 2022
Photocatalysis
has
captured
the
imagination
of
synthetic
chemists
and
is
poised
to
become
a
staple
fine
chemical
industry.
Over
past
decade,
subfield
energy-transfer
(EnT)
catalysis
expanded
dramatically,
harnessing
excited
states
photosensitizer
unlock
variety
redox-neutral,
radical-based
reactivities
in
mild
selective
fashion.
However,
many
developments
this
discipline
rely
on
precious
rare
earth
metals
such
as
iridium.
This
perspective
will
highlight
rise
thermally
activated
delayed
fluorescence
(TADF)
materials
metal-free
alternatives
EnT
photocatalysis
for
organic
transformations.
Emphasis
be
placed
recent
progress
cycloadditions,
E/Z
isomerization
olefins,
other
radical-initiated
processes;
all
mediated
by
mechanism
Dexter
energy
transfer.
The
tunable
excited-state
energetics
dynamics
TADF
allow
them
effectively
compete
with
iridium-based
sensitizers,
indicating
their
promise
green
organocatalysis.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(15)
Published: Jan. 28, 2023
Using
photocatalytic
oxidation
to
convert
basic
chemicals
into
high
value
compounds
in
environmentally
benign
reaction
media
is
a
current
focus
catalytic
research.
The
challenge
lies
gaining
controllability
over
product
formation
selectivity.
We
design
covalent
triazine
frameworks
as
heterogeneous,
metal-free,
and
recyclable
photocatalysts
for
visible-light-driven
switchable
selective
of
styrene
pure
water.
Selectivity
was
achieved
by
activation
or
deactivation
the
specific
photogenerated
oxygen
species.
same
photocatalyst,
H2
O2
,
benzaldehyde
obtained
with
99
%
conversion
selectivity
single
product.
highly
challenging
sensitive
epoxidation
carried
out
creating
peroxymonocarbonate
an
initial
agent
presence
bicarbonate,
which
led
oxide
up
76
near
quantitative
conversion.
This
study
demonstrates
preliminary
yet
interesting
example
simple
control
reactions
organic
Progress in Materials Science,
Journal Year:
2024,
Volume and Issue:
144, P. 101289 - 101289
Published: March 28, 2024
This
comprehensive
review
explores
the
potential
of
tailored
carbon
materials
(TCM)
for
efficient
photocatalytic
degradation
polyaromatic
hydrocarbons
(PAHs),
which
are
persistent
and
toxic
organic
pollutants
posing
significant
environmental
challenges.
The
unique
structure
properties
TCM
including
graphene
nanotubes
to
activated
dots,
have
projected
them
as
next-generation
technological
innovation.
A
careful
critical
discussion
state-of-the-art
research
sheds
light
on
their
effectiveness
in
catalyzing
breakdown
PAHs,
projects
suitable
management
environment.
Beyond
this
viewpoint,
article
expands
scope
1)
biomedical
healthcare,
2)
energy
storage
conversion,
3)
advanced
electronics.
challenges,
opportunities,
future
perspectives
related
role
applications,
inspiring
further
research,
innovation
photo-induced
techniques
also
carefully
discussed
article.
focused
serves
a
valuable
resource
researchers
industrialists
interested
harnessing
capabilities
carbon-based
sustainable
PAHs
other
pollutants.
It
addresses
pressing
need
effective
remediation
pollution
control
strategies.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(6), P. 4026 - 4035
Published: Feb. 1, 2024
Herein,
we
report
a
divergent
synthesis
of
fluoroalkyl
ketones
through
visible-light-induced
reactions
between
readily
available
organoboronic
esters
and
acylsilanes.
Selective
control
the
reactivity
in
situ
generated
organoboronate
complexes
is
key
to
achieving
transformations.
Under
basic
conditions,
undergo
deboronative
fluoride
elimination,
resulting
formation
enol
silyl
ethers
as
intermediates
that
react
with
various
electrophiles
generate
defluorinated
products.
Moreover,
combination
peroxide,
1,2-shift
group
favored
over
elimination
ketal
intermediates,
leading
This
transition-metal-free
reaction
operationally
simple,
aryl,
alkenyl,
alkyl
boronic
are
all
suitable
substrates.
The
synthetic
potential
has
been
demonstrated
by
gram-scale
facile
bioactive
molecules
including
zifrosilone
its
analogs.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 2, 2025
Regiodivergent
asymmetric
synthesis
represents
a
transformative
strategy
for
the
efficient
generation
of
structurally
diverse
chiral
products
from
single
set
starting
materials,
significantly
enriching
their
enantiomeric
composition.
However,
design
radical-mediated
regiodivergent
and
enantioselective
reactions
that
can
accommodate
wide
range
functional
groups
substrates
has
posed
significant
challenges.
The
obstacles
primarily
lie
in
switching
regioselectivity
achieving
high
enantiodiscrimination,
especially
when
dealing
with
high-energy
intermediates.
To
address
these
issues,
we
have
developed
new
catalytic
system
integrates
photoinduced
hydrogen
atom
transfer
(HAT)
copper
catalysis,
involving
fine-tuning
ligands,
additives,
other
reaction
parameters.
facilitates
cross-couplings
between
N-aryl
glycine
ester/amide
derivatives
abundant
hydrocarbon
feedstocks
through
strong
C(sp3)–H
bond
activation.
This
approach
allows
controlled
stereoselective
formation
C(sp3)–C(sp3)
C(sp3)–N
bonds,
yielding
rich
variety
C-
or
N-alkylated
esters
amides
commendable
yields
(up
to
92%
yield),
exclusive
regioselectivities
(typically
>20:1
rr),
enantioselectivities
96%
ee).
Our
methodology
not
only
provides
promising
avenue
incorporation
alkyl
functionalities
onto
specific
sites
biologically
molecules
but
also
offers
practical
while
simultaneously
induction
within
photochemical
reactions.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(31)
Published: May 25, 2022
Regiodivergent
alkene
functionalization
that
produces
either
regioisomer
starting
from
the
same
raw
materials
is
desirable.
Herein,
we
report
a
nickel-catalyzed
switchable
site-selective
hydroalkylation.
The
selection
of
reaction
temperatures
leads
to
protocols
provide
regiodivergent
hydroalkylated
products
single
substrate.
This
protocol
allows
convenient
synthesis
α-
and
β-branched
protected
amines,
both
which
are
important
fields
pharmaceutical
chemistry
biochemistry.
In
addition,
enantioenriched
alkylamines
can
be
accessed
in
catalytic
asymmetric
variant.
Preliminary
mechanistic
studies
indicate
formation
more
stable
nickelacycle
provides
driving
force
migration.
thermodynamic
kinetic
properties
different
reduction
elimination
intermediates
responsible
for
site-selectivity.
Chemical Science,
Journal Year:
2022,
Volume and Issue:
14(1), P. 149 - 161
Published: Dec. 1, 2022
By
combining
the
energy
input
from
two
red
photons,
chemical
reactions
that
would
normally
require
blue
or
ultraviolet
irradiation
become
accessible.
Key
advantages
of
this
biphotonic
excitation
strategy
are
light
usually
penetrates
deeper
into
complex
reaction
mixtures
and
causes
less
photo-damage
than
direct
illumination
in
ultraviolet.
Here,
we
demonstrate
primary
light-absorber
a
dual
photocatalytic
system
comprised
transition
metal-based
photosensitizer
an
organic
co-catalyst
can
completely
alter
outcome.
Photochemical
reductions
achieved
with
copper(i)
presence
sacrificial
electron
donor,
whereas
oxidative
substrate
activation
occurs
osmium(ii)
photosensitizer.
Based
on
time-resolved
laser
spectroscopy,
changeover
photochemical
reactivity
is
due
to
different
underlying
mechanisms.
Following
triplet
transfer
9,10-dicyanoanthracene
(DCA)
subsequent
triplet-triplet
annihilation
upconversion,
fluorescent
singlet
excited
state
DCA
triggers
activation,
which
initiates
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(36), P. 20141 - 20148
Published: Aug. 28, 2023
Chemodivergent
synthesis
has
been
achieved
in
asymmetric
photocatalysis.
Under
a
dual
catalyst
system
consisting
of
chiral
phosphoric
acid
and
DPZ
as
photosensitizer,
different
inorganic
bases
enabled
the
formation
two
sets
valuable
products
from
three-component
radical
tandem
transformations
2-bromo-1-arylenthan-1-ones,
styrenes,
quinoxalin-2(1H)-ones.
The
key
to
success
was
distinct
pKa
environment,
which
radicals
that
formed
on
quinoxalin-2(1H)-one
rings
after
addition
processes
underwent
either
single-electron
oxidation
or
reduction.
In
addition,
this
work
represents
first
use
quinoxalin-2(1H)-ones
photoredox
catalysis.
