While
photocatalysts
are
generally
responsible
for
radical
generation
from
bench
stable
diaryliodonium
salts,
recent
reports
have
emerged
exhibiting
photocatalyst-free
using
select
Lewis
bases
as
activators.
Herein,
we
demonstrate
1)
the
ability
of
numerous
to
enable
light-driven
and
2)
these
radicals
can
be
captured
by
transition-metals
coupling
reactions.
These
results
first
step
toward
developing
new
organometallic
aryl
reactions
without
photocatalysts.
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.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(43), P. 7900 - 7905
Published: Oct. 26, 2023
We
report
an
organophotoredox-catalyzed
stereoselective
allylic
arylation
of
MBH
acetates
with
a
palette
diaryliodonium
triflates
(DAIRs)
to
provide
the
corresponding
trisubstituted
alkenes
in
moderate
good
yields.
The
method
could
be
extended
three-component
coupling
involving
1,4-diazabicyclo[2.2.2]octane
bis(sulfur
dioxide)
adduct
(DABSO)
as
sulfur
dioxide
surrogate
for
synthesis
biologically
relevant
sulfones.
Both
these
reactions
were
carried
out
under
mild
conditions
featuring
broad
scope,
robustness,
and
appreciable
functional
group
tolerance.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
16(11)
Published: Jan. 15, 2024
Abstract
Visible‐light‐activated
organic
reactions
unlock
novel
avenues
for
complex
molecular
transformations,
impossible
under
standard
“thermal”
conditions,
which
makes
them
powerful
tools
in
the
arsenal
of
synthetic
chemistry.
However,
transition
metal‐based
or
photoredox
catalysts
are
often
used
to
ensure
productive
absorption
visible
light,
might
be
not
desirable
medicinal
chemistry
and
industry
due
toxicity,
low
sustainability,
high
cost
most
photocatalysts.
A
more
environmentally
economically
benign
approach
is
based
on
formation
transient
electron
donor‐acceptor
(EDA)
complexes
between
two
reagents
a
reagent
an
additive,
that
readily
absorb
acting
as
internal
photosensitizers.
Within
EDA
complex‐based
arylation
strategies,
chemical
transformations
mediated
by
noncovalent
interaction
molecules,
namely
electron‐poor
aryl
halides
their
equivalents
electron‐rich
nucleophilic
additives.
Moreover,
besides
stoichiometric
organocatalysis
can
achieved
certain
cases
through
regeneration
donor
molecules
course
reaction.
Photoexcitation
induces
single
transfer
(SET)
process
generate
radical
species
step.
This
Review
will
focus
state‐of‐the‐art
strategies
utilizing
halides,
aryldiazonium,
diaryliodonium,
arylsulfonium
arylphosphonium
salts
reactants,
published
mainly
last
five
years.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(11), P. 1893 - 1900
Published: May 20, 2023
Abstract
Arylation
of
amino‐,
diamino‐
and
triaminophosphines
with
aryl(mesityl)iodonium
triflates
under
blue
light
irradiation
followed
by
oxidative
P−N
bond
cleavage
in
the
situ
generated
amino
phosphonium
salts
hydrolytic
conditions
represent
a
method
for
synthesis
substituted
arylphosphine
oxides,
arylphosphinic
arylphosphonic
amides
respectively.
The
proposed
approach
is
based
on
using
visible
as
only
promoter
C−P
formation,
accommodates
variety
functional
groups,
can
be
applied
to
late‐stage
C−H
functionalization
drug
molecules.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(43)
Published: Sept. 5, 2023
Pnictogen
bonding
(PnB)
has
gained
recognition
as
an
appealing
strategy
for
constructing
novel
architectures
and
unlocking
new
properties.
Within
the
synthetic
community,
development
of
a
straightforward
much
simpler
protocol
cross-electrophile
C-PIII
coupling
remains
ongoing
challenge
with
organic
halides.
In
this
study,
we
present
simple
photoinduced
PnB-enabled
couplings
using
readily
available
chlorophosphines
halides
via
merging
single
electron
transfer
(SET)
halogen
atom
(XAT)
processes.
photomediated
transformation,
PnB
formed
between
alkyl
amines
facilitates
photogeneration
PIII
radicals
α-aminoalkyl
through
SET.
Subsequently,
resulting
activate
C-X
bonds
XAT,
leading
to
formation
carbon
radicals.
This
methodology
offers
operational
simplicity
compatibility
both
aliphatic
aromatic
Organic Letters,
Journal Year:
2025,
Volume and Issue:
27(4), P. 1012 - 1017
Published: Jan. 21, 2025
Vicinal
bis(tetraarylphosphonium)
salts
have
scarcely
been
reported
in
the
literature.
In
this
study,
we
demonstrate
that
visible-light-induced
difunctionalization
of
ortho-trifluoromethylsulfonylated
diaryliodonium
conveniently
furnishes
bis(phosphonium)
without
additional
catalysts
or
photoinitiators.
The
methodology
establishes
a
practical
platform
for
preparation
using
readily
available
tertiary
phosphines.
are
anticipated
to
garner
great
deal
interest
catalytic
and
medicinal
chemistry.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 20, 2025
A
novel
strategy
for
C-P
bond
formation
has
been
developed.
The
reaction
employed
aromatic
carboxylic
acids
as
the
source
of
groups
to
couple
with
three
types
P(O)-H(2)
compounds
without
need
isolate
intermediates,
thereby
achieving
a
one-pot
construction
carbon-phosphorus
bonds.
protocol
demonstrated
excellent
applicability
and
functional
group
tolerance,
enabling
production
Ar-P(O)R2
Ar2-PPh
moderate
yields.
Chemical Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 7, 2025
Constructing
chemical
bonds
under
green
sustainable
conditions
has
drawn
attention
from
environmental
and
economic
perspectives.
The
dissociation
of
(hetero)aryl-halide
is
a
crucial
step
most
arylations
affording
(hetero)arene
derivatives.
Herein,
we
summarize
the
(hetero)aryl
halides
activation
enabling
direct
(hetero)arylation
trapping
reagents
construction
highly
functionalized
(hetero)arenes
benign
conditions.
strategies
for
aryl
iodides
are
classified
into
(a)
hypervalent
iodoarene
followed
by
functionalization
thermal/photochemical
conditions,
(b)
aryl-I
bond
in
presence
bases
with/without
organic
catalysts
promoters,
(c)
photoinduced
presence/absence
organophotocatalysts,
(d)
electrochemical
direct/indirect
electrolysis
mediated
organocatalysts
mediators
acting
as
electron
shuttles,
(e)
electrophotochemical
redox-active
organocatalysts.
These
modes
result
exhibiting
diverse
reactivity
formal
cations/radicals/anions
aryne
precursors.
coupling
these
reactive
intermediates
with
leads
to
facile
selective
formation
C-C
C-heteroatom
bonds.
ecofriendly,
inexpensive,
functional
group-tolerant
offer
alternatives
transition
metal-based
catalysis.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(14), P. 9923 - 9928
Published: July 1, 2024
Diethyl
acetamidomalonate
(DEAM)
has
been
widely
used
for
the
synthesis
of
α-amino
acids
via
C-alkylation
under
basic
conditions
followed
by
hydrolysis/decarboxylation.
In
contrast,
C-arylation
this
reagent
remains
undeveloped.
Herein,
we
report
a
novel
strategy
racemic
α-arylglycines
based
on
selective
arylation
DEAM
with
diaryliodonium
salts
mild,
transition
metal-free
conditions.
The
reaction
features
good
functional
group
tolerance
and
easy
scalability
is
applicable
to
chemoselective
C-H-modification
arenes
including
approved
drugs,
thus
enabling
straightforward
approach
complex
that
would
be
challenging
make
otherwise.
