A
controllable
rhodium-catalyzed
formal
C−H
arylation
and
carbonylative
of
a
variety
readily
accessible
arenes
bearing
N-containing
heterocycles-directing
groups
aryl
halides
under
1
atm
carbon
monoxide
(CO)
was
developed.
Good
to
excellent
yields
various
bi(hetero)aryls
7-aroyl
indolines
were
obtained
using
different
substrates.
Preliminary
mechanistic
studies
support
that
proposed
carbonylation/decarbonylation
reaction
sequence
might
be
involved
in
the
arylation.
This
approach
features
high
efficiency,
good
functional
group
tolerance,
chemoselectivity,
offers
powerful
strategy
access
biaryls,
indoles
as
well.
The Chemical Record,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 29, 2025
Abstract
Carbazoles
are
an
important
class
of
nitrogen‐containing
heterocycles
found
in
diverse
natural
products,
bioactive
molecules,
and
functional
materials.
Their
broader
applications
have
driven
extensive
research
into
their
synthesis
functionalization.
Among
various
approaches,
transition
metal‐catalyzed
C−H
activation
has
emerged
as
a
powerful
tool
for
direct
functionalization,
offering
regioselectivity,
efficiency,
sustainability.
This
review
comprehensively
summarizes
advancements
functionalization
carbazoles.
Various
catalytic
systems
employing
palladium,
ruthenium,
rhodium,
nickel,
cobalt,
copper,
iron
enabled
alkylation,
alkenylation,
acylation,
arylation,
alkynylation,
heteroatom
incorporation
These
methodologies
late‐stage
diversification
opened
avenues
accessing
structurally
complex
carbazole
derivatives
with
tailored
properties.
The
aims
to
provide
comprehensive
guide
researchers
exploring
via
activation,
highlighting
key
mechanistic
insights,
scope,
emerging
trends
this
field.
Organic Letters,
Год журнала:
2023,
Номер
25(29), С. 5411 - 5415
Опубликована: Июль 17, 2023
A
cobalt(III)-catalyzed
directed
C-7
alkynylation
of
indolines
with
easily
accessible
bromoalkynes
has
been
developed.
The
reaction
a
broad
substrate
scope
excellent
yields
and
represents
powerful
route
to
the
synthesis
7-alkynyl-substituted
indolines.
In
addition,
can
be
extended
coupling
N-aryl
7-azaindoles,
highlighting
synthetic
practicability
strategy.
Organic & Biomolecular Chemistry,
Год журнала:
2022,
Номер
20(14), С. 2808 - 2812
Опубликована: Янв. 1, 2022
We
developed
a
rhodium-catalysed
decarbonylative
C(sp2)-H
alkylation
method
for
indolines.
This
reaction
facilitates
the
use
of
alkyl
carboxylic
acids
and
their
anhydrides
as
cheap,
abundant
non-toxic
source
under
redox-neutral
conditions,
featuring
introduction
primary
chain,
which
cannot
be
addressed
by
previous
radical-mediated
decarboxylative
reaction.
Through
mechanistic
investigation,
we
revealed
that
an
initially
formed
C-7
acylated
indoline
was
transformed
into
corresponding
alkylated
via
decarbonylation
process.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(9), С. 6159 - 6167
Опубликована: Апрель 17, 2023
Symmetrical
anhydrides
were
synthesized
from
activated
amides
such
as
N-benzoylsaccharins
and
N-Boc-protected
benzamides.
The
reacted
with
H2O
in
the
presence
of
1,4-diazabicyclo[2.2.2]octane
(DABCO)
at
25
°C
to
produce
corresponding
symmetrical
high
yields
through
C-N
bond
cleavage.
In
addition,
benzoic
acid
derivatives
generate
unsymmetrical
yields.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(8), С. 1840 - 1846
Опубликована: Фев. 8, 2024
Abstract
Herein,
we
report
a
chemo‐
and
regioselective
Rh‐catalyzed
redox
C7‐spiroannulation
reaction
of
N
‐benzo[
d
]imidazole
indolines
with
maleimides,
resulting
in
series
indoline
fused
azaspirocycles
up
to
92%
yield.
The
synthetic
utility
is
demonstrated
by
the
synthesis
highly
functionalized
nitrogen‐containing
spiropolycyclic
skeletons.
annulation
could
also
be
performed
maleic
esters
acrylates.
products
were
purified
simple
filtration.
Rh
catalyst
can
recycled,
at
gram‐scale
using
0.5
mol%
catalyst,
which
makes
this
protocol
potentially
applicable
industry.
Moreover,
efficient
post‐modification
pharmaceutical
molecules
demonstrates
its
practicability.
Organic Letters,
Год журнала:
2022,
Номер
24(43), С. 7997 - 8001
Опубликована: Окт. 27, 2022
Cu-catalyzed
cross-dehydrogenative
coupling
of
the
C7
C-H
bond
indolines
with
sulfoximines
has
been
accomplished.
The
reaction
can
be
extended
to
N-aryl
7-azaindoles
monoselectivity.
use
first-row
copper
catalysis,
substrate
scope,
and
late-stage
synthetic
applications
are
important
practical
features.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(40)
Опубликована: Июнь 18, 2024
Abstract
Carbazole
derivatives
are
vital
in
medicinal
and
materials
chemistry,
yet
accessing
diverse
substitutions
remains
challenging.
Here,
we
introduce
a
regioselective
approach
for
C1
C8
alkynylation
of
carbazoles
via
palladium‐catalyzed
C−H
activation.
This
method
provides
direct
route
to
mono‐
di‐alkynylated
derivatives,
addressing
the
scarcity
alkynylated
carbazole‐based
materials.
Our
study
broadens
synthetic
toolbox
carbazole
functionalization,
offering
potential
applications
optoelectronics,
bio‐imaging,
beyond,
while
contributing
developing
sustainable
activation
methodologies.
Synlett,
Год журнала:
2023,
Номер
34(16), С. 1894 - 1898
Опубликована: Май 8, 2023
Abstract
We
developed
a
novel
access
to
indoloindolone
by
rhodium-catalyzed
intramolecular
acylation
of
2-(indol-1-yl)benzoic
acids.
This
reaction
proceeds
via
the
in
situ
formation
mixed
anhydride
under
redox-neutral
conditions.
Preliminary
mechanistic
investigations
revealed
that
formed
participates
C–H
activation
step,
which
is
facilitated
RhI
catalyst.
The
utility
this
was
demonstrated
large-scale
reaction.
