Organic Letters,
Год журнала:
2024,
Номер
26(3), С. 676 - 680
Опубликована: Янв. 18, 2024
A
palladium-catalyzed
divergent
cascade
decarboxylative
annulation
of
aryl
iodides
and
α-oxocarboxylic
acids
using
norbornene
(NBE)
derivatives
as
a
controlled
switch
is
reported.
When
NBE
used
mediator,
fluorenones
are
synthesized
with
moderate
to
excellent
yields
via
Catellani
reaction
that
involves
sequential
ortho-C–H
arylation
ipso-decarboxylative
acylation
iodides.
Employing
oxanorbornadiene
(ONBD)
instead
enables
the
assembly
dibenzo[a,c]cycloheptenones
by
retro-Diels–Alder
rather
than
release
an
ONBD.
Additionally,
synthetic
utility
this
method
demonstrated
diversification
products.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(45)
Опубликована: Июль 25, 2024
Abstract
C−H
bond
functionalization
involving
C
,
‐palladacycle
intermediates
provides
a
unique
platform
for
developing
novel
reactions.
However,
the
vast
majority
of
studies
have
been
limited
to
transformations
(aryl),
‐palladacycles.
In
sharp
contrast,
catalytic
reactions
(alkyl),
(alkyl)‐palladacycles
rarely
reported.
Herein,
we
disclose
an
unprecedented
cascade
C(sp
3
)−H
annulation
(alkyl)‐palladacycles.
this
protocol,
alkene‐tethered
cycloalkenyl
bromides
undergo
intramolecular
Heck/C(sp
activation
generate
(alkyl)‐palladacycles,
which
can
be
captured
by
α
‐bromoacrylic
acids
afford
tricyclic
fused
pyridinediones.
addition,
strategy
also
applied
indole‐tethered
construct
pentacyclic
pyridinediones
via
suquential
Heck
dearomatization/C(sp
activation/decarboxylative
cyclization.
Notably,
removal
in
reaction
build
interesting
skeleton
containing
four‐membered
ring.
Preliminary
mechanistic
experiments
indicate
that
five‐membered
serve
as
key
intermediates.
Meanwhile,
density
functional
theory
(DFT)
calculations
provided
insights
into
pathway.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(21), С. 2614 - 2620
Опубликована: Июль 3, 2024
Comprehensive
Summary
Concise
assembly
of
spirooxindoles
is
great
significance
but
a
challenging
task
in
modern
organic
synthesis.
Described
herein
an
unusual
base‐promoted
[4+2]
spiroannulation
rarely
used
isatin‐derived
β‐silylcarbinols
with
o
‐halogen
aromatic
ketones,
which
enables
rapid
and
modular
synthesis
six‐membered
carbocyclic
high
yields
excellent
functional
group
tolerance
(>
50
examples).
Mechanistic
experiments
revealed
that
this
reaction
involved
Peterson
olefination,
Michael
addition
intramolecular
C(sp
3
)
arylation
cascade.
The
variegated
synthetic
derivatization
target
products
successful
construction
bioactive
molecules
further
illustrate
the
potential
spirooxindole‐related
drug
discovery.
Molecules,
Год журнала:
2024,
Номер
29(22), С. 5265 - 5265
Опубликована: Ноя. 7, 2024
Sequential
Pd-catalyzed
one-pot
synthetic
methodologies
have
emerged
as
a
powerful
and
versatile
approach
in
organic
synthesis,
enabling
the
construction
of
complex
heterocyclic
architectures
with
high
efficiency,
selectivity,
atom
economy.
This
review
discusses
key
advancements
multistep,
sequentially
processes
for
accessing
derivatives,
focusing
on
classic
reactions
like
Suzuki-Miyaura,
Sonogashira,
Heck,
hydroamination
extending
to
specialized
techniques
such
directed
C-H
activation.
The
concatenation
these
steps
has
advanced
scope
strategies.
A
section
is
dedicated
exploring
cooperative
use
palladium
other
metals,
particularly
copper,
ruthenium,
gold,
which
broadened
range
accessible
derivatives.
Highlighted
applications
include
synthesis
biologically
pharmaceutically
relevant
compounds,
tris(hetero)aryl
systems,
spiro-oxindoles,
indole
These
strategies
not
only
streamline
but
also
align
green
chemistry
principles
by
minimizing
purification
reducing
waste
energy
consumption.
addresses
current
challenges
limitations
methodologies,
offering
insights
into
ongoing
efforts
optimize
reaction
conditions
expand
applicability
sequential
processes.
Organic Letters,
Год журнала:
2023,
Номер
25(28), С. 5361 - 5365
Опубликована: Июль 12, 2023
The
palladium-catalyzed
synthesis
of
bis-heterocyclic
spirocycles
containing
both
pyrroline
and
indoline
motifs
is
reported.
Di-tert-butyldiaziridinone
used
to
functionalize
palladacycles
generated
in
situ
via
domino
Narasaka–Heck/C–H
activation
reactions.
reaction
readily
scalable,
the
spirocyclic
products
can
undergo
deprotection,
reduction,
(3
+
2)
cycloadditions,
highlighting
their
synthetic
utility.
Additionally,
kinetic
isotope
effect
experiments
support
a
turnover-limiting
C–H
functionalization
step
catalytic
cycle.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(11), С. 1203 - 1208
Опубликована: Фев. 6, 2024
Comprehensive
Summary
Herein,
we
report
an
efficient
and
practical
protocol
for
the
photoinduced
dehalocyclization
of
ortho
‐halophenylacrylamides
with
formate
by
engagement
a
CO
2
radical
anion
to
access
substituted
oxindoles.
This
method
proceeds
smoothly
under
mild
conditions
exhibits
wide
range
substrate
as
well
remarkable
functional
group
compatibility.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(16), С. 11793 - 11800
Опубликована: Июль 29, 2023
A
palladium-catalyzed
multicomponent
cascade
reaction
of
aryl
iodides,
oxanorbornadiene,
and
diborns
to
access
(Z)-alkenylborons
is
reported.
This
transformation
proceeds
through
the
sequential
carbopalladation/boronation/retro-Diels-Alder
domino
reaction.
The
oxanorbornadiene
used
in
this
serves
as
an
acetylene
surrogate,
which
generated
via
a
retro-Diels-Alder
Such
stereoselective
scalable
approach
has
wide
range
functional
group
tolerance
good
substrate
universality.
Organic Letters,
Год журнала:
2024,
Номер
26(24), С. 5069 - 5073
Опубликована: Июнь 7, 2024
We
have
demonstrated
a
Pd(0)-catalyzed
Heck/C(sp3)–H
activation
cascade
for
the
synthesis
of
spirocyclopropyl
oxindoles
in
high
yields
from
easily
accessible
ortho-bromoacrylamides.
The
formation
oxindole
is
guided
by
an
unconventional
four-membered
palladacycle
through
C(sp3)–H
activation.
reaction
exhibits
wide
range
substrate
scope
and
operates
efficiently
with
mere
0.5
mol
%
Pd-catalyst.
In
addition,
use
microwave
conditions
facilitates
rapid
completion
reaction.
Furthermore,
this
spirocyclopropanation
strategy
can
be
coupled
[3
+
2]
cycloaddition
to
produce
spiropyrrolidine
oxindoles,
offering
valuable
approach
preparation
alkaloids
such
as
(±)-horsfiline
(±)-coerulescine.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
11(2), С. 348 - 357
Опубликована: Ноя. 22, 2023
Divergent
synthesis
of
spirooxindoles
and
furan-containing
oxindoles
via
base-controlled
palladium
catalysis
was
achieved.
The
key
intermediates,
allene
insertion,
Pd–carbene
migratory
insertion
are
supported
by
DFT
calculations.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 18, 2024
2-Methylquinazolin-4(3H)-ones
were
efficiently
constructed
using
solid
calcium
carbide
as
an
alkyne
source,
2-aminobenzamides
or
2-aminobenzohydrazides
substrates,
and
p-tolylsulfonyl
azide
a
mediator
through
simultaneous
formation
of
two
C–N
bonds
in
one
step.
The
salient
features
this
protocol
are
the
use
inexpensive,
abundant
easy-to-use
source
substitute
for
flammable
explosive
gaseous
acetylene,
low-cost
catalyst,
wide
substrate
scope,
satisfactory
yield,
simple
manipulation.
This
method
can
also
be
extended
to
gram
scale.
