The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(13), P. 9249 - 9256
Published: June 23, 2023
Here,
we
report
the
first
case
of
nickel-catalyzed
C–H
cyanation
via
arylthianthrenium
salts.
The
reaction
features
use
air-stable
and
inexpensive
NiCl2·6H2O
as
a
catalyst
for
highly
selective
construction
products
by
aromatic
pre-thianthrenation.
mechanism
study
shows
that
formation
aryl
radicals
is
involved.
Also,
this
protocol
can
be
applied
to
late-stage
functionalization
bioactive
molecules
readily
scalable,
further
showcasing
synthetic
utility.
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(46), P. 13690 - 13707
Published: Jan. 1, 2022
This
review
summarizes
the
synthesis
of
diverse
organothianthrenium
salts
from
various
precursors
and
their
applications
in
organic
to
forge
new
C–C,
C–H
C–heteroatom
bonds
by
C–S
bond
cleavage
with
different
mechanistic
considerations.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(36), P. 5343 - 5364
Published: Jan. 1, 2023
The
activation
and
transformation
of
organic
chemical
bonds
is
a
fundamental
scientific
problem.
In
the
past
several
decades,
C-S
bond
cleavage
for
construction
C-C
C-heteroatom
has
received
tremendous
attention
in
chemistry.
Although
significant
progress
been
made
field
transition
metal
strategies,
variety
novel
transition-metal-free
strategies
have
also
developed
using
halogenated
reagents,
oxidants,
acids,
bases.
Moreover,
photochemical
electrochemical
methods
to
achieve
organosulfur
compounds.
To
date,
however,
no
comprehensive
review
reported.
Therefore,
we
herein
provide
major
advances
compounds,
including
thioethers,
sulfoxides,
sulfones,
thioacetals,
sulfonium
salts,
sulfur
ylides.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(9), P. 1845 - 1850
Published: Feb. 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
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Jan. 15, 2024
Abstract
Direct
and
site-selective
C-H
functionalization
of
alkenes
under
environmentally
benign
conditions
represents
a
useful
attractive
yet
challenging
transformation
to
access
value-added
molecules.
Herein,
unified
protocol
for
variety
intermolecular
Heck-type
functionalizations
C
sp2
-H
bond
has
been
developed
by
thianthrenation.
The
reaction
features
metal-free
operationally
simple
exclusive
cine
-selective
aliphatic
aryl
forge
C-C,
C-N,
C-P,
C-S
bonds
at
room
temperature,
providing
general
with
nucleophiles
(Nu
=
sulfinates,
cyanides,
amines,
amides).
Alkenes
undergo
-sulfonylation,
cyanation,
amination
afford
alkenyl
sulfones,
nitriles
enamines.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(41)
Published: Aug. 17, 2022
Three-membered
cyclic
structures
are
widely
existing
in
natural
products
and
serve
as
enabling
intermediates
organic
synthesis.
However,
the
efficient
straightforward
access
to
such
with
diversity
remains
a
formidable
challenge.
Herein,
general
practical
protocol
aziridines
cyclopropanes
synthesis
using
free
XH2
(X=C
or
N)
alkenes
by
thianthrenation
is
presented.
This
metal-free
features
direct
aziridination
cyclopropanation
unprotected
.
Free
sulfonamides,
amides,
carbamates,
amines,
methylene
acidic
protons,
good
precursors,
providing
an
attractive
alternative
for
of
from
easily
available
starting
materials.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(15), P. 8299 - 8307
Published: April 6, 2023
Modular
strategies
to
rapidly
increase
molecular
complexity
have
proven
immensely
synthetically
valuable.
In
principle,
transformation
of
an
alkene
into
a
dielectrophile
presents
opportunity
deliver
two
unique
nucleophiles
across
alkene.
Unfortunately,
the
selectivity
profiles
known
dielectrophiles
largely
precluded
this
deceptively
simple
synthetic
approach.
Herein,
we
demonstrate
that
dicationic
adducts
generated
through
electrolysis
alkenes
and
thianthrene
possess
profile
relative
more
conventional
dielectrophiles.
Specifically,
these
species
undergo
single
perfectly
regioselective
substitution
reaction
with
phthalimide
salts.
This
observation
unlocks
appealing
new
platform
for
aminofunctionalization
reactions.
As
illustrative
example,
implement
reactivity
paradigm
address
longstanding
challenge:
diamination
distinct
nitrogen
nucleophiles.
Studies
mechanism
process
reveal
key
alkenyl
thianthrenium
salt
intermediate
controls
exquisite
regioselectivity
highlight
importance
proton
sources
in
controlling
sulfonium
electrophiles.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(19)
Published: March 18, 2024
Abstract
Unnatural
amino
acids,
and
their
synthesis
by
the
late‐stage
functionalization
(LSF)
of
peptides,
play
a
crucial
role
in
areas
such
as
drug
design
discovery.
Historically,
LSF
biomolecules
has
predominantly
utilized
traditional
synthetic
methodologies
that
exploit
nucleophilic
residues,
cysteine,
lysine
or
tyrosine.
Herein,
we
present
photocatalytic
hydroarylation
process
targeting
electrophilic
residue
dehydroalanine
(Dha).
This
possesses
an
α
,
β
‐unsaturated
moiety
can
be
combined
with
various
arylthianthrenium
salts,
both
batch
flow
reactors.
Notably,
setup
proved
instrumental
for
efficient
scale‐up,
paving
way
unnatural
acids
peptides
substantial
quantities.
Our
approach,
being
inherently
mild,
permits
diversification
even
when
they
contain
sensitive
functional
groups.
The
readily
available
salts
facilitate
seamless
integration
Dha‐containing
wide
range
arenes,
blueprints,
natural
products,
culminating
creation
unconventional
phenylalanine
derivatives.
synergistic
effect
high
group
tolerance
modular
characteristic
aryl
electrophile
enables
peptide
conjugation
ligation
conditions.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(16)
Published: Feb. 8, 2024
Oxidative
alkene
functionalization
reactions
are
a
fundamental
class
of
complexity-building
organic
transformations.
However,
the
majority
established
approaches
rely
on
electrophilic
reagents
that
limit
diversity
groups
can
be
installed.
Recent
advances
have
new
approach
instead
relies
transformation
alkenes
into
thianthrene-derived
cationic
electrophiles.
These
linchpin
intermediates
generated
selectively
and
undergo
diverse
array
mechanistically
distinct
with
abundant
nucleophiles.
Taken
together,
this
unlocks
suite
net
oxidative
transformations
been
elusive
using
conventional
strategies.
This
Minireview
describes
these
is
organized
around
three
synthons
formally
accessible
from
via
thianthrenation:
1)
alkenyl
cations;
2)
vicinal
dications;
3)
allyl
cations.
Throughout
Minireview,
we
illustrate
how
thianthrenium
salts
address
key
limitations
endemic
to
classic
alkene-derived
electrophiles
highlight
mechanistic
origins
distinctions
wherever
possible.