Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(37), P. 7949 - 7955
Published: Sept. 11, 2024
A
novel
electron
donor-acceptor
(EDA)
complex/copper
catalysis
model
has
been
proposed
for
the
construction
of
2,3-diarylpropionitriles
under
visible
light
conditions.
The
developed
protocol
proceeds
via
intermolecular
charge
transfer
between
photoactive
EDA
complex
dibutamine
(DBA),
aryl
thianthrenium
salts,
and
trimethylsilyl
cyanide
(TMSCN),
followed
by
a
copper
catalytic
cycle.
UV-vis
absorption
measurements
confirm
participation
complexes
as
reactive
intermediates.
This
three-component
process
smoothly
in
presence
pharmaceutically
relevant
core
structures
sensitive
functional
groups,
which
offers
possibility
precise
editing
drug
molecules
with
important
scaffolds.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(29)
Published: March 24, 2023
Abstract
The
photoactivation
of
electron
donor‐acceptor
complexes
has
emerged
as
a
sustainable,
selective
and
versatile
strategy
for
the
generation
radical
species.
Electron
(EDA)
complexation,
however,
imposes
electronic
constraints
on
donor
acceptor
components
this
can
limit
range
radicals
that
be
generated
using
approach.
New
EDA
complexation
strategies
exploiting
sulfonium
salts
allow
to
from
native
functionality.
For
example,
aryl
salts,
formed
by
activation
arenes,
serve
in
due
their
electron‐deficient
nature.
This
“sulfonium
tag”
approach
relaxes
parent
substrate
dramatically
expands
complexation.
In
review,
these
new
applications
will
introduced
areas
chemical
space
rendered
accessible
through
innovation
highlighted.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(15), P. 9653 - 9675
Published: July 11, 2023
The
activation
and
utilization
of
substrates
mediated
by
Frustrated
Lewis
Pairs
(FLPs)
was
initially
believed
to
occur
solely
via
a
two-electron,
cooperative
mechanism.
More
recently,
the
occurrence
single-electron
transfer
(SET)
from
base
acid
observed,
indicating
that
mechanisms
proceed
one-electron-transfer
processes
are
also
feasible.
As
such,
SET
in
FLP
systems
leads
formation
radical
ion
pairs,
which
have
recently
been
more
frequently
observed.
In
this
review,
we
aim
discuss
seminal
findings
regarding
established
insights
into
chemistry
as
well
highlight
examples
process.
addition,
applications
reported
main
group
radicals
will
be
reviewed
discussed
context
understanding
systems.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(43)
Published: Sept. 13, 2023
Abstract
The
utilization
of
aryl
radicals
as
open‐shelled
intermediates
has
become
an
essential
tool
for
both
conventional
and
state‐of‐the‐art
synthetic
chemistry.
However,
the
current
methods
generating
are
still
inefficient,
greatly
impeding
their
practical
applications.
Encouragingly,
sulfonium
salts
have
emerged
appealing
sources
a
wide
range
transformations
aimed
at
creating
novel
chemical
bonds
driven
by
distinctive
structural
attributes
tendencies.
This
review
primarily
focuses
on
specific
reaction
mechanisms
underlying
cleavage
C−S
in
salts,
leading
to
generation
corresponding
within
diverse
conditions.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(46), P. 8290 - 8295
Published: Nov. 14, 2023
We
report
a
photoredox
system
comprising
sodium
iodide,
triphenyl
phosphine,
and
N,N,N',N'-tetramethylethylenediamine
(TMEDA)
that
can
form
self-assembled
tetrameric
electron
donor-acceptor
(EDA)
complex
with
diaryliodonium
reagents
(DAIRs)
furnish
aryl
radicals
upon
visible
light
irradiation.
This
practical
mode
of
activation
DAIRs
enables
arylation
an
array
heterocycles
under
mild
conditions
to
provide
the
respective
heteroaryl-(hetero)aryl
assembly
in
moderate
excellent
yields.
Detailed
mechanistic
investigations
photophysical
DFT
studies
provided
insight
into
reaction
mechanism.
Chem,
Journal Year:
2024,
Volume and Issue:
10(4), P. 1240 - 1251
Published: Feb. 13, 2024
The
photoactivation
of
sulfonium
salt
EDA
(electron
donor-acceptor)
complexes
provides
a
mild
platform
for
aryl-radical-mediated
halogen
atom
transfer
activation
wide
range
functionalized
alkyl
iodides,
including
tertiary
iodides.
Using
an
aryl
with
carbonate
as
inexpensive
donor
complex
formation,
the
general
reaction
has
been
applied
in
divergent,
metal-free
photochemical
approach
to
nitriles
and
amides.
This
divergency
was
made
possible
by
tuning
isocyanide
radical
traps.
For
example,
identification
readily
accessible,
bench-stable,
crystalline
amide
containing
grants
access
nitrile
products
complete
selectivity.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Feb. 29, 2024
Abstract
The
photochemical
properties
of
Electron
Donor-Acceptor
(EDA)
complexes
present
exciting
opportunities
for
synthetic
chemistry.
However,
these
strategies
often
require
an
inert
atmosphere
to
maintain
high
efficiency.
Herein,
we
develop
EDA
complex
photocatalytic
system
through
rational
design,
which
overcomes
the
oxygen-sensitive
limitation
traditional
systems
and
enables
aerobic
oxygenation
reactions
dioxygen
activation.
mild
oxidation
transfers
electrons
from
donor
effective
catalytic
acceptor
upon
visible
light
irradiation,
are
subsequently
captured
by
molecular
oxygen
form
superoxide
radical
ion,
as
demonstrated
specific
fluorescent
probe,
dihydroethidine
(DHE).
Furthermore,
this
visible-light
mediated
oxidative
protocol
is
successfully
applied
in
boronic
acids.
We
believe
that
activation
strategy
enabled
not
only
provides
a
practical
approach
but
also
promotes
design
application
photocatalysis
under
ambient
conditions.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(12), P. 7198 - 7205
Published: Jan. 1, 2024
In
situ
-generated
protonated
aromatic
hydrocarbons
overcome
their
intrinsic
electronic
properties
to
serve
as
catalytic
electron
acceptors,
avoiding
the
use
of
photocatalysts,
metals,
and
redox
reagents
achieve
fluoroalkylation.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(3), P. 728 - 733
Published: Jan. 12, 2024
Carboxylic
functionalities
are
among
the
pivotal
groups
in
bioactive
molecules
and
synthesis
of
new
lead
compounds
because
their
unique
character
formation
hydrogen
bonds
possibility
constructing
molecular
complexes
via
amide
couplings.
We
adopt
reductive
radical-polar
crossover
strategy
to
introduce
carboxyalkyl
into
arenes
with
styrenes
CO2
thianthrenium
salts.
This
protocol
exhibits
excellent
potential
as
a
straightforward
modular
platform
for
site-selective
carboxylative
derivation
molecules.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(16), P. 5938 - 5943
Published: Jan. 1, 2024
Cyclopropyl-substituted
sulfonium
salts
are
obtained
by
Rh-catalysed
addition
of
α-diazo
dibenzothiophenium
to
olefins.
When
indenes
used
as
substrates,
initially
formed
cyclopropyl
rings
open
with
concomitant
elimination
dibenzothiophene,
enabling
access
2-substituted
naphthalenes.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: April 10, 2024
The
photoredox
electron
donor-acceptor
(EDA)
complex-mediated
radical
coupling
reaction
has
gained
prominence
in
the
field
of
organic
synthesis,
finding
widespread
application
two-component
reactions.
However,
EDA
complex-promoted
multi-component
reactions
are
not
well
developed
with
only
a
limited
number
examples
have
been
reported.
Herein,
we
report
photoinduced
and
highly
chemoselective
three-component
arylalkylation
[1.1.1]propellane,
which
allows
direct
functionalization
C(sp
