Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Июнь 3, 2024
Abstract
A
dearomative
oxidation
of
pyrroles
to
Δ
3
‐pyrrol‐2‐ones
is
described,
which
employs
a
sulfoxide
as
oxidant,
in
conjunction
with
carboxylic
acid
anhydride
and
Brønsted
additive.
3‐substituted
undergo
regioselective
give
the
product
isomer
oxygen
has
been
introduced
at
more
hindered
position.
Regioselectivity
rationalized
by
proposed
mechanism
that
proceeds
initial
thianthrenium
introduction
less‐hindered
pyrrole
α‐position,
followed
distal
attack
an
nucleophile
subsequent
elimination
thianthrene.
The
same
reaction
conditions
are
also
able
effect
chemoselective
indoles
indolin‐3‐ones
additionally
2‐hydroxyindolin‐3‐ones.
Here
again,
regio‐
chemoselectivities
through
intermediacy
salt.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(12), С. 3333 - 3340
Опубликована: Янв. 1, 2024
We
report
a
Pd/NBE
cooperative
catalyzed
ortho
C–H
methylation
and
trideuteromethylation
of
arylthianthrenium
salts,
enabling
the
efficient
synthesis
wide
variety
(trideutero)methylated
arenes
in
moderate
to
good
yields.
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.
Organic Letters,
Год журнала:
2024,
Номер
26(31), С. 6681 - 6686
Опубликована: Июль 26, 2024
Here,
we
demonstrate
palladium-catalyzed
Hiyama-type
cross-coupling
reactions
of
aryl
thianthrenium
or
phenoxathiinium
salts.
By
employing
stable
and
inexpensive
organosilanes,
the
arylation,
alkenylation,
alkynylation
were
realized
in
high
efficiency
using
commercially
available
Pd(tBu3P)2
as
catalyst,
thus
providing
a
reliable
method
for
preparation
biaryls,
styrenes,
acetylenes
with
broad
functional
group
tolerance
under
mild
conditions.
Given
accessibility
salts
from
simple
arenes
remarkable
regioselective
fashion,
this
protocol
also
provides
an
attractive
approach
late-stage
modification
complex
bioactive
scaffolds.
ACS Catalysis,
Год журнала:
2024,
Номер
14(16), С. 12181 - 12191
Опубликована: Июль 30, 2024
The
advancement
of
sophisticated
synthetic
methodologies
that
streamline
reaction
processes
while
enhancing
molecular
complexity
is
a
perpetual
necessity
in
the
realm
chemistry.
Catalytic
one-pot
cascade
play
crucial
role
efficient
construction
intricate
molecules
with
exceptional
chemoselectivity.
Herein,
we
present
approach
for
synthesis
polycyclic
fused
δ-lactams
via
sequential
phosgenation,
Pd/NBE-catalyzed
ortho-carbamoylation/ipso-Heck-type
cyclization,
and
C–H
activation
from
readily
available
aryl
halides,
amines,
triphosgenes.
This
stands
out
as
first
example
situ
carbamoyl
chloride
formation
amine
precursors,
presenting
an
alternative
to
existing
transformations
involving
chlorides.
practical
significance
these
showcased
by
81
rapid
economically
favorable
manner,
without
need
intermediate
purification.
Moreover,
were
scalable
compatible
various
natural
products
pharmaceuticals,
further
underscoring
effectiveness
this
strategy.
relatively
rigid
coplanar
structure
displayed
our
synthesized
exhibits
distinct
room-temperature
phosphorescence
characteristics,
which
have
been
utilized
anticounterfeiting
high-security-level
data
encryption.
Angewandte Chemie International Edition,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 11, 2025
While
the
palladium/norbornene
(Pd/NBE)
cooperative
catalysis
has
become
increasingly
useful
for
arene
functionalization,
its
substrate
scope
been
mainly
restricted
to
reactive
aryl
iodides
and
bromides.
Despite
being
a
more
available
attractive
feedstock,
common
chlorides
have
not
used
as
substrates
Pd/NBE
catalysis.
Herein
we
report
first
general
Pd/NBE-catalyzed
vicinal
difunctionalization
of
chlorides.
Enabled
by
combination
secondary-amide-substituted
NBEs
XPhos
ligand,
diverse
can
now
undergo
successful
ortho
alkylation,
amination,
acylation
with
different
ipso
terminations,
including
olefination,
hydrogenation,
alkynylation.
To
show
utility
this
method,
late-stage
derivatizations
complex
bioactive
compounds
sequential
functionalizations
polyhaloarenes
achieved.
Angewandte Chemie,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 11, 2025
Abstract
While
the
palladium/norbornene
(Pd/NBE)
cooperative
catalysis
has
become
increasingly
useful
for
arene
functionalization,
its
substrate
scope
been
mainly
restricted
to
reactive
aryl
iodides
and
bromides.
Despite
being
a
more
available
attractive
feedstock,
common
chlorides
have
not
used
as
substrates
Pd/NBE
catalysis.
Herein,
we
report
first
general
Pd/NBE‐catalyzed
vicinal
difunctionalization
of
chlorides.
Enabled
by
combination
secondary‐amide‐substituted
NBEs
XPhos
ligand,
diverse
can
now
undergo
successful
ortho
alkylation,
amination,
acylation
with
different
ipso
terminations,
including
olefination,
hydrogenation,
alkynylation.
To
show
utility
this
method,
late‐stage
derivatizations
complex
bioactive
compounds
sequential
functionalizations
polyhaloarenes
achieved.
