Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 16, 2024
Given
that
(hetero)aryl
carboxylic
acids
are
inexpensive
materials
available
in
a
great
variety
from
commercial
and
natural
resources
or
synthesis,
the
strategies
enabling
their
use
as
starting
for
preparing
fine
chemicals
highly
sought
after.
Here
we
report
photoinduced
Cu(II)-mediated
protocol
converting
into
thianthrenium
salts,
high
value-added
building
blocks
can
undergo
various
subsequent
transformations,
creating
an
attractive
two-step
pathway
divergent
functionalization
of
these
ubiquitous
materials.
The
excellent
compatibility
method
is
shown
by
broad
range
sterically
electronically
varied
including
derivatives
pharmaceuticals,
such
ataluren,
celecoxib,
flavoxate,
probenecid,
repaglinide,
tamibarotene.
syntheses
13
C-labeled
probenecid
bioisosteres
ataluren
well
unconventional
modifications
celecoxib
illustrate
synthetic
potential
strategy.
Mechanistic
studies
line
with
reaction
occurring
through
ligand-to-metal
charge
transfer
(LMCT)
Cu(II)-arylcarboxylates,
radical
decarboxylative
carbometallation
to
form
arylcopper(II)
intermediates
turn
react
thianthrene
product.
Noteworthy,
susceptibility
aryl
salts
photodegradation
overcome
Cu(I)-driven
salvage
loop,
which
continuously
intercepts
transiently
formed
radicals
regenerates
products.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(25), P. 13542 - 13548
Published: June 12, 2023
The
arylethylamine
pharmacophore
is
conserved
across
a
range
of
biologically
active
natural
products
and
pharmaceuticals,
particularly
in
molecules
that
act
on
the
central
nervous
system.
Herein,
we
present
photoinduced
copper-catalyzed
azidoarylation
alkenes
at
late
stage
with
arylthianthrenium
salts,
allowing
access
to
highly
functionalized
acyclic
(hetero)arylethylamine
scaffolds
are
otherwise
difficult
access.
A
mechanistic
study
consistent
rac-BINAP-CuI-azide
(2)
as
photoactive
catalytic
species.
We
show
utility
new
method
by
expedient
synthesis
racemic
melphalan
four
steps
through
C-H
functionalization.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(9), P. 1813 - 1818
Published: Feb. 22, 2024
Herein,
we
present
a
novel
Catellani-type
reaction
that
employed
aryl-thianthrenium
salts
as
aryl
substrates
to
trigger
the
subsequent
palladium/norbornene
cooperatively
catalyzed
progress.
This
strategy
can
achieve
site-selective
C–H
difunctionalization
of
compounds
without
directing
groups
or
known
initiating
reagent.
A
series
functionalized
syntheses
bioactive
molecules
further
demonstrated
potential
this
strategy.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 21, 2025
Thianthrenation
is
a
useful
strategy
for
the
late-stage
diversification
of
complex
small
molecules
owing
to
positional
selectivity
and
synthetic
versatility
thianthrenium
salts
as
electrophilic
linchpins.
However,
substrate-dependent
identification
suitable
reaction
conditions
thianthrenation
can
be
difficult.
Reported
functionalization
vary
significantly
and,
in
some
instances,
lack
robustness
practicality.
Herein,
we
report
generalized
approach
preparation
two
manifolds
practical,
robust,
parallel
salts.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(20), P. 3784 - 3789
Published: May 16, 2023
An
efficient
strategy
for
the
preparation
of
aryl
phosphonates
via
blue-light-promoted
single
electron
transfer
process
an
EDA
complex
between
phosphites
and
thianthrenium
salts
has
been
demonstrated.
The
corresponding
substituted
were
obtained
in
good
to
excellent
yields,
byproduct
thianthrene
can
be
recovered
reused
quantity.
This
developed
method
realizes
construction
through
indirect
C-H
functionalization
arenes,
which
potential
application
value
drug
discovery
development.
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:
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.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(44)
Published: Sept. 13, 2023
Abstract
Efficient
methods
for
synthesizing
1,2‐aryl(alkenyl)
heteroatomic
cores,
encompassing
heteroatoms
such
as
nitrogen,
oxygen,
sulfur,
and
halogens,
are
of
significant
importance
in
medicinal
chemistry
pharmaceutical
research.
In
this
study,
we
present
a
mild,
versatile
practical
photoredox/iron
dual
catalytic
system
that
enables
access
to
highly
privileged
pharmacophores
with
exceptional
efficiency
site
selectivity.
Our
approach
exhibits
an
extensive
scope,
allowing
the
direct
utilization
wide
range
commodity
or
commercially
available
(hetero)arenes
well
activated
unactivated
alkenes
diverse
functional
groups,
drug
scaffolds,
natural
product
motifs
substrates.
By
merging
iron
catalysis
photoredox
cycle,
vast
array
alkene
functionalization
products
incorporate
neighboring
azido,
amino,
halo,
thiocyano
nitrooxy
group
were
secured.
The
scalability
ability
rapid
synthesize
numerous
bioactive
small
molecules
from
readily
starting
materials
highlight
utility
protocol.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(16), P. 3332 - 3337
Published: April 15, 2024
As
a
class
of
rising
electrophilic
coupling
reagents,
aryl–thianthreniums
(aryl-TTs)
have
been
gaining
immense
attention.
Herein,
novel
palladium-catalyzed
domino
annulation
aryl-TTs
with
anhydrides
is
proposed
to
rapidly
assemble
collection
highly
functionalized
fluorenones.
This
finding
presents
an
innovative
reaction
pattern
wherein
the
version
first
involved.
Heavily
compared
existing
conversions
aryl-TTs,
this
identified
process
successively
functions
as
four
aryl
C–H
bonds.