ACS Catalysis,
Год журнала:
2024,
Номер
14(4), С. 2664 - 2670
Опубликована: Фев. 6, 2024
A
light-driven
method
for
the
generation
of
aryl
radicals
from
triarylbismuth(III)
and
(V)
reagents
is
described.
Aryl
radical
proposed
to
occur
through
ligand-assisted
mesolytic
cleavage
an
organobismuth(IV)
intermediate
generated
either
oxidation
BiIII
or
reduction
BiV.
This
mode
demonstrated
be
compatible
with
a
range
bimolecular
arylations,
including
hydroarylation
electron-deficient
olefins
arylation
diboronates,
disulfides,
sulfonyl
cyanides,
phosphites,
isocyanides.
The
intermediacy
supported
by
trapping
clock
experiments,
BiIV–aryl
mesolysis
computationally.
Chemical Reviews,
Год журнала:
2021,
Номер
122(2), С. 2292 - 2352
Опубликована: Дек. 9, 2021
The
halogen-atom
transfer
(XAT)
is
one
of
the
most
important
and
applied
processes
for
generation
carbon
radicals
in
synthetic
chemistry.
In
this
review,
we
summarize
highlight
aspects
associated
with
XAT
impact
it
has
had
on
photochemistry
photocatalysis.
organization
material
starts
analysis
mechanistic
then
follows
a
subdivision
based
nature
reagents
used
halogen
abstraction.
This
review
aims
to
provide
general
overview
fundamental
concepts
main
agents
involved
objective
offering
tool
understand
facilitate
development
new
radical
strategies.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(13), С. 7587 - 7680
Опубликована: Янв. 1, 2021
Organic
compounds
that
show
Thermally
Activated
Delayed
Fluorescence
(TADF)
have
become
wildly
popular
as
next
generation
emitters
in
organic
light-emitting
diodes
(OLEDs),
but
since
2016,
received
significant
and
increasing
attention
photocatalysts.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(36), С. 19526 - 19549
Опубликована: Апрель 22, 2021
The
use
of
organic
photocatalysts
has
revolutionized
the
field
photoredox
catalysis,
as
it
allows
access
to
reactivities
that
were
traditionally
restricted
transition-metal
photocatalysts.
This
Minireview
reports
recent
developments
in
acridinium
ions
and
cyanoarene
derivatives
synthesis.
activation
inert
chemical
bonds
well
late-stage
functionalization
biorelevant
molecules
are
discussed,
with
a
special
focus
on
their
mechanistic
aspects.
Organic Letters,
Год журнала:
2021,
Номер
23(8), С. 2976 - 2980
Опубликована: Март 29, 2021
A
general
and
metal-free
visible-light-induced
decarboxylative
arylation
procedure
at
room
temperature
was
described
for
the
construction
of
acylated
heterocyclic
derivatives,
such
as
benzimidazo/indolo[2,1-a]isoquinolin-6(5H)-ones,
aroylazaspiro[4.5]trienones,
thioflavones,
so
on.
This
practical
conducted
by
using
2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile
(4CzIPN)
a
photocatalyst
under
mild
conditions,
which
avoided
use
an
additional
base,
traditional
heating,
metal
reagents.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Янв. 6, 2023
Cyanoarene-based
photocatalysts
(PCs)
have
attracted
significant
interest
owing
to
their
superior
catalytic
performance
for
radical
anion
mediated
photoredox
catalysis.
However,
the
factors
affecting
formation
and
degradation
of
cyanoarene-based
PC
(PC•‒)
are
still
insufficiently
understood.
Herein,
we
therefore
investigate
PC•‒
under
widely-used
photoredox-mediated
reaction
conditions.
By
screening
various
PCs,
elucidate
strategies
efficiently
generate
with
adequate
excited-state
reduction
potentials
(Ered*)
via
supra-efficient
generation
long-lived
triplet
excited
states
(T1).
To
thoroughly
behavior
in
actual
reactions,
a
reductive
dehalogenation
is
carried
out
as
model
identified
dominant
photodegradation
pathways
PC•‒.
Dehalogenation
coexistent
depending
on
rate
electron
transfer
(ET)
substrate
strongly
depends
electronic
steric
properties
PCs.
Based
understanding
both
PC•‒,
demonstrate
that
efficient
highly
reducing
allows
catalyzed
aryl/alkyl
halides
at
loading
low
0.001
mol%
high
oxygen
tolerance.
The
present
work
provides
new
insights
into
reactions
reactions.
Green Chemistry,
Год журнала:
2023,
Номер
25(5), С. 1975 - 1981
Опубликована: Янв. 1, 2023
This
study
describes
a
green
and
sustainable
photoinduced
strategy
for
decarboxylative
C–H
(amino)alkylation
of
heteroarenes
with
carboxylic
acids
under
metal-
photosensitizer-free
conditions.
ACS Catalysis,
Год журнала:
2024,
Номер
14(8), С. 6247 - 6258
Опубликована: Апрель 10, 2024
Aryl-substituted
bicyclo[1.1.1]pentane
(BCP-aryl)
derivatives
represent
the
most
important
bioisosteres
of
biaryl
scaffolds
and
widely
exist
in
numerous
complex
pharmaceutical
molecules.
The
current
synthetic
method
limitations
using
only
tertiary
radical
precursors,
prefunctionalized
heteroarenes,
toxic
transition
metals,
expensive
photocatalysts
make
it
urgent
to
develop
a
more
simple
practical
protocol.
To
confront
enrich
Minisci-type
chemistry,
herein,
we
disclose
photocatalytic
multicomponent
reaction
for
synthesis
various
(halo)alkyl
BCP-aryls
[1.1.1]propellane,
alkyl
halides,
unfunctionalized
heteroarenes
as
starting
materials.
Diverse
kinds
radicals
(primary,
secondary,
carbons)
derived
from
chlorides,
bromides,
fluoroalkyl
iodides
are
very
compatible
this
transformation.
practicability
is
additionally
boosted
by
product
derivatizations
late-stage
functionalization
pharmaceutically
relevant
mechanistic
studies
demonstrate
that
relay
mechanism
initiated
consecutive
photoinduced
electron
transfer
(ConPET)
process
operation.
We
anticipate
methodology
would
act
useful
tool
biaryl-type
drug
derivatives,
ultimately
resulting
great
utility
discovery
program.
Organic Letters,
Год журнала:
2024,
Номер
26(4), С. 883 - 888
Опубликована: Янв. 22, 2024
Herein,
we
present
a
transition-metal-free,
easy
handling
protocol
for
regioselective
carboxylation
of
gem-difluorostyrenes
with
sodium
formate
as
the
C1
source.
30
examples
α-fluoracrylates
were
obtained
in
yields
to
80%
under
these
conditions.
A
defluorinative
monofluorovinyl
intermediate
and
consecutive
photoinduced
electron
transfer
mechanism
proposed
after
investigation.
Green Chemistry,
Год журнала:
2022,
Номер
24(19), С. 7403 - 7409
Опубликована: Янв. 1, 2022
Redox-neutral
ketyl
couplings:
a
metal-
and
additive-free
ConPET
photocatalytic
system
allows
highly
efficient
coupling/cyclization
of
N
-aryl
acrylamides
carbonyls
with
formal
100%
atom
economy.
