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.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(61)
Published: Aug. 26, 2024
In
recent
times,
diaryliodonium
reagents
(DAIRs)
have
witnessed
a
resurgence
as
arylating
reagents,
especially
under
photoinduced
conditions.
However,
reactions
proceeding
through
electron
donor-acceptor
(EDA)
complex
formation
with
DAIRs
are
restricted
to
electron-rich
reacting
partners
serving
donors
due
the
well-known
cage
effect.
We
discovered
practical
and
high-yielding
visible-light-induced
EDA
platform
generate
aryl
radicals
from
corresponding
use
them
synthesize
key
chalcogenides.
this
process,
an
array
of
dichalcogenides
react
in
presence
1,4
diazabicyclo[2.2.2]octane
(DABCO)
cheap
readily
available
donor,
furnishing
variety
di(hetero)aryl
aryl/alkyl
chalcogenides
good
yields.
The
method
is
scalable,
features
broad
scope
yields,
operates
open-to-air
chalcogenation
technology
suitable
for
late-stage
functionalizations
disulfide
bioconjugations
facilitates
access
biologically
relevant
thioesters,
dithiocarbamates,
sulfoximines,
sulfones.
Moreover,
applies
synthesizing
diverse
pharmaceuticals,
such
vortioxetine,
promazine,
mequitazine,
dapsone,
amenable
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(24)
Published: Feb. 19, 2024
Abstract
Quaternary
N
‐aryl‐DABCO
salts
were
introduced
for
the
first
time
as
a
highly
selective
sensing
platform
thiols
and
selenols.
By
employing
this
platform,
sensitive
coumarin
based
“off‐on”
fluorescent
probe
was
designed
synthesized.
The
possesses
good
solubility
in
water,
low
background
fluorescence,
and,
most
importantly,
demonstrates
high
selectivity
to
aryl
selenols
over
their
aliphatic
counterparts
other
common
nucleophiles.
A
dramatic
increase
fluorescence
intensity
is
achieved
through
cleavage
of
quaternized
DABCO‐ring,
yielding
piperazine
derivatives
with
quantum
yield
(~72
%).
Moreover,
stability
used
reducing
agents
DTT
TCEP
demonstrated.
limits
detection
p
‐thiocresol
phenyl
selenide
evaluated
be
22
nM
6
nM,
respectively.
Herein,
we
demonstrate
1)
that
Lewis
base
heteroatom
coordination
to
diaryliodonium
salts
is
not
required
for
light-driven
radical
generation
and
2)
radicals
generated
by
this
route
can
be
captured
transition-metals
coupling
reactions.
These
results
are
the
first
step
toward
developing
new
aryl
reactions
without
exogenous
photocatalysts.
We
demonstrate
1)
that
halogen
bonding
is
not
critical
for
enabling
light-driven
radical
generation
from
diaryliodonium
salts
and
2)
radi-cals
generated
by
this
route
can
be
captured
transition-metals
C–H
arylation
reactions.
These
results
are
the
first
step
toward
devel-oping
new
metal-catalyzed
aryl
couplings
without
exogenous
photocatalysts.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(54), P. 6929 - 6932
Published: Jan. 1, 2024
We
demonstrate
(1)
detectable
halogen
bonding
is
not
critical
for
enabling
light-driven
radical
generation
from
diaryliodonium
salts
and
(2)
radicals
generated
by
this
route
can
be
captured
transition-metals
C-H
arylation
reactions.
These
results
are
the
first
step
toward
developing
new
metal-catalyzed
aryl
couplings
without
exogenous
photocatalysts.
Diaryliodonium
salts
are
bench
stable
aryl
radical
precursors.
While
photocatalysts
generally
responsible
for
generation,
recent
reports
have
emerged
exhibiting
photocatalyst-free
generation
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
reactions
without
photocatalysts.
Abstract
A
metal‐
and
irradiation‐free
approach
for
the
direct
arylation
of
secondary
phosphines
has
been
developed.
The
reaction
employs
diaryliodonium
salts
as
electrophilic
aryl‐transfer
reagents,
effecting
P−Ar
bond‐formation
in
a
single
step,
under
mild
conditions,
using
t
‐BuOK
base
DMSO
solvent.
protocol
furnishes
expedient
access
to
diverse
unsymmetrical
triarylphosphines
and,
upon
one‐pot
oxidation,
corresponding
triarylphosphine
oxides.
Experimental
computational
studies
support
inner
sphere
mechanism
through
reductive
coupling
at
hypervalent
iodine
center.
calculations
also
point
key
role
played
by
potassium
ions,
providing
extra
stabilization
P−C
bond‐forming
transition
state
binding
reactants
via
cation‐π
interactions.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 6, 2024
Abstract
Most
of
the
reported
work
focus
on
development
O
‐,
N
C
‐
and
S
‐glycosylation
methods.
However,
no
study
explores
P(III)‐glycosylation
reaction.
Herein
we
describe
a
convenient
protocol
to
realize
process.
A
simple
β
‐phosphino
ester
is
adopted
as
P(III)‐transfer
reagent
for
this
new
type
glycosylation
via
nucleophilic
substitution
release
strategy.
Diverse
phosphine
units
are
introduced
anomeric
center
various
sugars
efficiently
with
excellent
stereoselectivity.
The
value
method
showcased
by
prepared
P(III)‐sugars
novel
linkers
in
bioactive
molecule
conjugation,
chiral
ligands
metal‐catalyzed
asymmetric
allylic
substitutions
organocatalysts.
Preliminary
mechanistic
studies
corroborated
designed
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 6, 2024
Abstract
Most
of
the
reported
work
focus
on
development
O
‐,
N
C
‐
and
S
‐glycosylation
methods.
However,
no
study
explores
P(III)‐glycosylation
reaction.
Herein
we
describe
a
convenient
protocol
to
realize
process.
A
simple
β
‐phosphino
ester
is
adopted
as
P(III)‐transfer
reagent
for
this
new
type
glycosylation
via
nucleophilic
substitution
release
strategy.
Diverse
phosphine
units
are
introduced
anomeric
center
various
sugars
efficiently
with
excellent
stereoselectivity.
The
value
method
showcased
by
prepared
P(III)‐sugars
novel
linkers
in
bioactive
molecule
conjugation,
chiral
ligands
metal‐catalyzed
asymmetric
allylic
substitutions
organocatalysts.
Preliminary
mechanistic
studies
corroborated
designed
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(43)
Published: Sept. 5, 2023
Abstract
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−P
III
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
P
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
