The
atom
transfer
radical
addition
(ATRA)
reaction
is
defined
as
a
method
for
introducing
halogenated
compounds
into
alkenes
via
mechanism.
In
this
study,
we
present
an
ATRA
approach
achieving
regioselective
functionalization
of
quinoxalin-2(1H)-ones
by
activating
C-Br
bonds
CBr4,
and
subsequent
trihaloalkyl-carbofunctionalization
styrenes
employing
the
9-mesityl-10-methylacridinium
perchlorate
(Fukuzumi)
photocatalyst
under
3W
blue
LED
(450-470
nm)
irradiation.
This
three-component
cascade
process
demonstrates
remarkable
efficiency
in
synthesis
1-methyl-3-(3,3,3-tribromo-1-(4-chlorophenyl)propyl)quinoxalin-2(1H)-one
derivatives.
ChemCatChem,
Journal Year:
2023,
Volume and Issue:
15(21)
Published: Aug. 14, 2023
Abstract
The
merging
of
photocatalysis
with
halogen‐atom
transfer
(XAT)
processes
has
proven
to
be
a
versatile
tool
for
the
generation
carbon‐centered
radicals
in
organic
synthesis.
XAT
are
unique
that
they
generate
without
requiring
use
strong
reductants
necessary
traditional
single
electron
(SET)
activation
halides.
Pathways
achieve
synthetic
applications
can
categorized
into
three
major
sections:
i)
heteroatom‐based
activators,
ii)
metal‐based
and
iii)
carbon‐based
activators
among
which
α‐aminoalkyl
have
taken
center
stage.
Access
these
as
reagents
gained
significant
attention
past
few
years
due
robustness
reactions,
simplicity
required,
broadness
their
applications.
Generation
is
simply
achieved
through
oxidation
tertiary
amines,
after
deprotonation
at
α‐position
generates
radicals.
Due
wide
scope
amines
available
tunable
nucleophilicity
radical
formed,
this
strategy
become
an
attractive
alternative
heteroatom/metal‐based
XAT.
In
minireview,
we
focus
our
on
recent
(2020–2023)
developments
uses
robust
technology
mediate
processes.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(3), P. 1784 - 1796
Published: Jan. 12, 2024
The
atom
transfer
radical
addition
(ATRA)
reaction
is
defined
as
a
method
for
introducing
halogenated
compounds
into
alkenes
via
mechanism.
In
this
study,
we
present
an
ATRA
approach
achieving
regioselective
functionalization
of
quinoxalin-2(1H)-ones
by
activating
C–Br
bonds
CBr4
and
subsequent
trihaloalkyl-carbofunctionalization
styrenes
employing
the
9-mesityl-10-methylacridinium
perchlorate
(Fukuzumi)
photocatalyst
under
3W
blue
LED
(450–470
nm)
irradiation.
This
three-component
cascade
process
demonstrates
remarkable
efficiency
in
synthesis
1-methyl-3-(3,3,3-tribromo-1-(4-chlorophenyl)propyl)quinoxalin-2(1H)-one
derivatives.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 8, 2025
The
temperature-dependent
switching
behavior
of
the
saccharin
radical
is
demonstrated,
enabling
regiodivergent
C3–H
and
C7–H
functionalization
quinoxalin-2(1H)-ones.
was
generated
through
N–Br
bond
cleavage
in
N-bromosaccharin
(NBSA)
observed
to
transition
between
radicophile
roles.
At
−10
°C,
it
utilized
as
a
radicophile,
resulting
100%
C3-amination,
while
at
+35
acted
radical,
leading
exclusive
C7-bromination.
Radical
nucleophilicity
controlled
by
temperature
modulation.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 27, 2025
In
this
work,
we
developed
a
general
catalytic
strategy
that
allows
Minisci
C-H
alkylation
of
variety
heterocycles
using
unactivated
alkyl
halide
as
an
radical
source
under
visible
light
photocatalysis.
Mild
reaction
conditions,
employing
4CzIPN
organophotocatalyst
and
aerial
oxygen
green
terminal
oxidant,
broad
scope,
good
functional
group
tolerance,
late-stage
bioactive
pharmaceutically
relevant
molecules
are
advantages
the
protocol.
Preliminary
mechanistic
studies
indicate
involvement
α-amino
further
our
conditions.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(17)
Published: March 19, 2024
Abstract
Herein
we
report
a
visible‐light‐induced
trifluoromethylative
difunctionalization
of
styrenes
and
phenylacetylenes
using
trifluoromethyl
thianthrenium
triflate
(TT‐CF
3
+
OTf
−
).
The
transformation
was
enabled
by
the
discovery
photoactive
catalytic
EDA
complex
formed
between
carbazolyl
dithiocarbamate
TT‐CF
.
This
three‐component
reactivity
platform
establishes
new
paradigm
for
,
significantly
expanding
its
repertoire
photochemically
trifluoromethylation
reactions.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(19)
Published: March 21, 2024
Abstract
Herein,
visible‐light‐induced
metal‐free
three‐component
amidoheteroarylation
of
alkenes
with
quinoxalin‐2(1
H
)‐ones
and
N‐sulfonylaminopyridinium
salts
is
developed.
This
protocol
involves
a
radical
relay
process
in
which
the
N‐centered
radicals
undergo
chemoselective
addition
to
form
an
alkyl
that
selectively
combines
heteroarenes,
leading
formation
C−C
C−N
bonds
one
step
under
mild
reaction
conditions.
The
involved
high
efficiency
selectivity,
wide
substrate
scope,
excellent
functional‐group
compatibility
demonstrate
practicability
developed
protocol.
Organic & Biomolecular Chemistry,
Journal Year:
2023,
Volume and Issue:
21(35), P. 7079 - 7084
Published: Jan. 1, 2023
Polychloromethylative
cyclization
of
N-alkenyl
indoles
was
developed
under
metal-free
conditions
to
afford
tricyclic
pyridoindolones
and
pyrroloindolones
in
moderate
good
yields.
In
the
reaction,
commercially
available
CHCl3
CH2Cl2
were
employed
as
tri-
dichloromethyl
radical
sources.
Moreover,
dichloromethylated
polycyclic
benzoimidazoles
can
also
be
obtained
standard
conditions.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(36)
Published: June 6, 2024
We
present
the
strategic
design
of
donor-acceptor
cyanoarene-based
photocatalysts
(PCs)
aiming
to
augment
beneficial
PC
degradation
for
halogen
atom
transfer
(XAT)-induced
dehalogenation
reactions.
Our
investigation
reveals
a
competitive
nature
between
catalytic
cycle
and
pathway,
with
becoming
dominant,
particularly
less
activated
alkyl
halides.
The
behavior
PCs
significantly
impacts
efficiency
XAT
process,
leading
exploration
into
manipulating
in
desirable
direction.
Recognizing
variation
rate
degradation,
as
well
its
influence
on
reaction
across
range
structures,
we
carefully
engineered
develop
pre-catalyst,
named
3DP-DCDP-IPN.
This
pre-catalyst
undergoes
rapid
an
active
form,
3DP-DCDP-Me-BN,
exhibited
enhanced
reducing
ability
radical
anion
form
induce
better
regeneration
consequently
effectively
catalyzes
reaction,
even
challenging
substrate.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(36)
Published: June 6, 2024
Abstract
We
present
the
strategic
design
of
donor‐acceptor
cyanoarene‐based
photocatalysts
(PCs)
aiming
to
augment
beneficial
PC
degradation
for
halogen
atom
transfer
(XAT)‐induced
dehalogenation
reactions.
Our
investigation
reveals
a
competitive
nature
between
catalytic
cycle
and
pathway,
with
becoming
dominant,
particularly
less
activated
alkyl
halides.
The
behavior
PCs
significantly
impacts
efficiency
XAT
process,
leading
exploration
into
manipulating
in
desirable
direction.
Recognizing
variation
rate
degradation,
as
well
its
influence
on
reaction
across
range
structures,
we
carefully
engineered
develop
pre‐catalyst,
named
3DP‐DCDP‐IPN.
This
pre‐catalyst
undergoes
rapid
an
active
form,
3DP‐DCDP‐Me‐BN,
exhibited
enhanced
reducing
ability
radical
anion
form
induce
better
regeneration
consequently
effectively
catalyzes
reaction,
even
challenging
substrate.
