Abstract
Palladium-
and
nickel-catalyzed
cross-couplings
are
powerful
methods
for
constructing
C–C
C–N
bonds,
particularly
through
Suzuki–Miyaura
Buchwald–Hartwig
reactions.
Although
aryl
iodides,
bromides,
triflates
the
most
commonly
used
substrates,
chlorides
less
frequently
utilized
due
to
their
lower
reactivity.
However,
they
appealing
because
readily
available
inexpensive.
This
short
review
highlights
recent
developments
on
of
chlorides,
using
both
homogeneous
heterogeneous
catalysis
with
palladium
nickel.
1
Introduction
2
Cross-Couplings
2.1
Homogeneous
Palladium
Catalysis
2.2
Heterogeneous
2.3
Nickel
2.4
3
Amination
Reactions
3.1
3.2
3.3
3.4
4
Conclusion
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(7), С. 4109 - 4118
Опубликована: Фев. 13, 2023
A
catalytic
approach
of
synthesizing
the
cis-selective
saturated
carbo-
and
heterocyclic
germanium
compounds
(3D
framework)
is
reported
via
hydrogenation
readily
accessible
aromatic
germanes
(2D
framework).
Among
numerous
catalysts
tested,
Nishimura's
catalyst
(Rh2O3/PtO2·H2O)
exhibited
best
reactivity
with
an
isolated
yield
up
to
96%.
broad
range
substrates
including
synthesis
unprecedented
was
explored.
This
selective
strategy
could
tolerate
several
functional
groups
such
as
−CF3,
−OR,
−F,
−Bpin,
−SiR3
groups.
The
synthesized
products
demonstrated
applications
in
coupling
reactions
newly
developed
aza-Giese-type
addition
reaction
(C–N
bond
formation)
from
cyclic
germane
product.
These
versatile
motifs
can
have
a
substantial
value
organic
medicinal
chemistry
they
show
orthogonal
while
competing
other
partners
boranes
or
silanes,
acquiring
three-dimensional
structure
high
stability
robustness.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(22), С. 15596 - 15608
Опубликована: Май 21, 2024
Transition
metal-catalyzed
alkene
isomerization
is
an
enabling
technology
used
to
install
distal
its
original
site.
Due
their
well-defined
structure,
homogeneous
catalysts
can
be
fine-tuned
optimize
reactivity,
stereoselectivity,
and
positional
selectivity,
but
they
often
suffer
from
instability
nonrecyclability.
Heterogeneous
are
generally
highly
robust
continue
lack
active-site
specificity
challenging
rationally
improve
through
structural
modification.
Known
single-site
heterogeneous
for
utilize
precious
metals
bespoke,
expensive,
synthetically
intense
supports.
Additionally,
have
mediocre
inspiring
us
develop
a
catalyst
with
active
site
made
readily
available
compounds
of
Earth-abundant
elements.
Previous
work
demonstrated
that
very
formed
upon
protonation
Ni[P(OEt)3]4
by
H2SO4,
generating
[Ni–H]+
This
incredibly
active,
also
decomposes
readily,
which
severely
limits
utility.
Herein
we
show
using
solid
acid
(sulfated
zirconia,
SZO300),
not
only
this
decomposition
prevented,
high
activity
maintained,
improved
selectivity
achieved,
broader
scope
functional
groups
tolerated.
Preliminary
mechanistic
experiments
suggest
the
catalytic
reaction
likely
goes
intermolecular,
two-electron
pathway.
A
detailed
kinetic
study
comparing
state-of-the-art
Ni
Pd
reveals
highest
seen
Ni/SZO300
system.
The
reactivity
Ni/SZO300,
limited
isomerization;
it
competent
hydroalkenylation,
hydroboration,
hydrosilylation,
demonstrating
broad
application
catalyst.
Suzuki-Miyaura
coupling
is
a
robust
method
for
constructing
C-C
bonds.
Typically,
stoichiometric
amounts
of
base
are
required.
However,
high
pH
conditions
can
lead
to
the
protodeboronation
several
substrates
and
generate
waste
salt
from
additive
base.
Here,
we
present
Pd-amine
co-immobilized
catalyst
enabling
SMC
with
catalytic
amount
base;
cross-coupling
product
was
18
times
higher
than
that
amines.
Furthermore,
use
amine
hydrophobic
alkyl
chain
water-based
solvent
effectively
removed
acid
byproducts
Pd
active
species
on
support
surface,
resulting
in
yield.
The
immobilized
characterized
by
elemental
analysis,
solid-state
NMR,
X-ray
absorption
fine
structure
spectroscopy.
Additionally,
photoelectron
spectroscopy,
powder
diffractometry,
transmission
electron
microscopy
measurements
revealed
situ
formation
nanoparticles
as
species.
Crucially,
this
system
facilitates
reactions
even
presence
aryl
halides
acidic
substituents.
Nanoscale Advances,
Год журнала:
2023,
Номер
5(9), С. 2621 - 2638
Опубликована: Янв. 1, 2023
A
novel
supramolecular
Pd(
ii
)
catalyst
supported
on
chitosan
grafted
by
l
-asparagine
using
EDTA
linker
was
prepared
and
successfully
employed
in
the
Heck
cross-coupling
reaction
to
afford
corresponding
cinnamic
acids
good
excellent
yields.
Cell Reports Physical Science,
Год журнала:
2023,
Номер
4(9), С. 101548 - 101548
Опубликована: Авг. 21, 2023
This
perspective
provides
an
entry-level
conversation
concerning
base
metal
catalysis
as
a
green
and
sustainable
solution
in
industrial
academic
contexts.
We
establish
definition
of
"base
metal,"
challenging
readers
to
consider
the
ethical
implications
sourcing.
explore
what
it
means
be
"sustainable"
provide
information
on
current
efforts
synthetic
chemistry.
examples
catalytic
trends
transformations
popular
fields
such
cross-coupling
small-molecule
conversion,
highlighting
relevant
systems.
Finally,
we
social
context—for
example,
decisions
related
catalyst
development
are
often
driven
by
factors
including
costliness,
safety,
adoptability
(whether
society
will
accept
its
usage),
performance.
How
do
move
forefront?
Is
concerned
if
materials
fabricated
from
cheaper
more
abundant
sources?
does
chemistry
community
guide
this
knowledge
translation?
