C-H
Functionalization
of
heteroarenes
stands
as
a
potent
instrument
in
organic
synthesis,
and
with
the
incorporation
visible
light,
it
emerged
transformative
game-changer.
In
this
domain,
electron
donor-acceptor
(EDA)
complex,
formed
through
pairing
an
electron-rich
substrate
electron-accepting
molecule,
has
garnered
substantial
consideration
recent
years
due
to
related
avoidance
requirement
photocatalyst
well
oxidant.
EDA
complexes
can
undergo
photoactivation
under
mild
conditions
exhibit
high
functional
group
tolerance,
making
them
potentially
suitable
for
functionalization
biologically
relevant
heteroarenes.
This
review
article
provides
overview
advancements
field
via
complex
literature
coverage
up
April,
2024.
Organic Letters,
Год журнала:
2024,
Номер
26(9), С. 1845 - 1850
Опубликована: Фев. 26, 2024
The
difunctionalization
of
alkenes
using
aryl
thianthrenium
salts
as
the
sources
has
been
reported
sporadically.
However,
four-component
on
basis
not
thus
far
and
still
remains
a
challenge.
Herein,
visible
light/copper
catalysis-enabled
reaction
salts,
DABCO·(SO
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(43)
Опубликована: Сен. 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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Апрель 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
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(8), С. 2195 - 2200
Опубликована: Янв. 1, 2024
A
Heck-like
coupling
of
cyclic
sulfonium
salts
with
alkenes
via
selective
C–S
bond
cleavage
using
a
copper
complex
as
photosensitizer
through
visible-light-driven
redox-neutral
process
has
been
developed.
Organic Letters,
Год журнала:
2024,
Номер
26(31), С. 6652 - 6657
Опубликована: Июль 26, 2024
We
report
a
visible-light-promoted
cyclization/sulfonylation
cascade
of
N-heterocycles
with
thianthrenium
salts
using
DABSO
as
the
SO2
surrogate.
This
method
features
excellent
functional
group
tolerance,
wide
substrate
scope,
and
late-stage
elaboration
bioactive
relevant
molecules.
Mechanistic
investigations
reveal
that
photoactive
electron
donor–acceptor
(EDA)
complexes
between
DABCO
are
capable
generation
aryl
radicals,
which
induce
following
insertion
by
attacking
DABSO,
thus
triggering
key
radical
cyclization
step.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(10), С. 2344 - 2351
Опубликована: Апрель 5, 2024
Abstract
A
process
for
the
synthesis
of
aryl
thioglycosides
from
thianthrenium
salts
and
1‐thiosugars
is
achieved
by
copper(I)‐mediated,
photoredox‐catalyzed
reactions.
The
desired
products
could
be
obtained
in
32%
to
78%
yield
after
irradiation
with
34
W
blue
light
at
room
temperature.
Various
functional
groups,
especially
including
halogen
were
well
tolerated
under
standard
reaction
conditions.
This
strategy
differs
conceptually
all
previous
S
‐glycosylations
that
thiosugar
functionality
incorporated
into
complex
natural
or
drugs
a
late
stage
site‐selectively,
which
has
not
been
shown
via
halides
aryldiazonium
salts.
RSC Advances,
Год журнала:
2023,
Номер
13(33), С. 23359 - 23364
Опубликована: Янв. 1, 2023
Aryl
phosphonates
are
accessed
by
visible-light
irradiation
of
new
EDA
complex
between
thianthrenium
salts
as
electron-acceptors
and
phosphites
electron-donor
molecules.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(30)
Опубликована: Май 7, 2024
Abstract
Site‐selective
ortho/ipso
C−H
difunctionalizations
of
aromatic
compounds
were
designed
to
afford
polyfunctionalized
arenes
including
challenging
1,2,3,4‐tetrasubstituted
ones
(62
examples,
up
97
%
yields).
To
ensure
the
excellent
regioselectivity
process
while
keeping
high
efficiency,
an
original
strategy
based
on
a
“C−H
thianthenation/Catellani‐type
reaction”
sequence
was
developed
starting
from
simple
arenes.
Non‐prefunctionalized
first
regioselectively
converted
into
corresponding
thianthrenium
salts.
Then,
palladium‐catalyzed,
norbornene
(NBE)‐mediated
allowed
synthesis
ipso
‐olefinated/
ortho
‐alkylated
using
thianthrene
as
leaving
group
(revisited
Catellani
reaction).
Pleasingly,
commercially
available
(NBE)
and
unique
catalytic
system,
synthetic
challenges
known
for
reaction
with
aryl
iodides
smoothly
successfully
tackled
“thianthrenium”
approach.
The
protocol
robust
(gram‐scale
reaction)
widely
applied
two‐fold
functionalization
various
bio‐active
compounds.
Moreover,
panel
olefins
alkyl
halides
coupling
partners
suitable.
further
incorporation
other
groups
at
(CN/alkyl/H,
aryl)
(alkyl,
aryl,
amine,
thiol)
positions,
showcasing
generality
process.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(17), С. 12668 - 12680
Опубликована: Авг. 9, 2024
Incorporating
a
sulfonyl
group
into
parent
molecules
has
been
shown
to
effectively
improve
their
synthetic
applications
and
bioactivities.
In
this
study,
we
present
straightforward
practical
approach
for
the
ring-opening
reaction
of
alkenyl–aryl
sulfonium
salts
with
sodium
sulfinates
produce
range
sulfur-containing
alkyl
sulfones.
This
method
offers
benefits
mild
conditions,
easily
accessible
raw
materials,
wide
substrate
applicability,
good
functional
compatibility,
operational
simplicity.
Importantly,
resulting
products
can
be
readily
converted
sulfoxides,
sulfones,
sulfoximines,
some
heterocyclic
compounds.
