ACS Catalysis,
Journal Year:
2018,
Volume and Issue:
8(8), P. 7228 - 7250
Published: June 20, 2018
The
Ni-catalyzed
Csp2–N
cross-coupling
of
NH
substrates
and
(hetero)aryl
(pseudo)halides
for
the
synthesis
(hetero)anilines
is
in
midst
a
resurgence.
Reactivity
breakthroughs
that
have
been
achieved
this
field
within
past
five
years
served
to
establish
Ni
catalysis
as
being
competitive
with,
some
cases
superior
to,
more
well-established
Pd-
or
Cu-based
protocols.
Whereas
repurposing
useful
ancillary
ligands
from
Pd
domain
has
most
frequently
employed
approach
quest
develop
effective
Ni-based
catalysts
such
transformations,
considerable
progress
made
late
design
tailored
specifically
use
with
Ni.
Bisphosphine
proven
be
well-suited
an
approach,
given
their
modular
facile
syntheses;
several
variants
emerged
recently
are
particularly
enabling
range
otherwise
challenging
cross-couplings.
This
Perspective
presents
comprehensive
summary
advancements
through
application
bisphosphine
ligand
class.
It
our
intention
discussion
key
concepts
mechanistic
considerations
presented
herein
will
provide
platform
researchers
initiate
efforts
development
high-performing
catalysts.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(15), P. 6307 - 6416
Published: Jan. 1, 2022
This
review
highlights
the
recent
advances
of
metalated
covalent
organic
frameworks,
including
synthetic
strategies
and
applications,
discusses
current
challenges
future
directions.
Chemical Reviews,
Journal Year:
2019,
Volume and Issue:
119(13), P. 8192 - 8228
Published: June 11, 2019
At
the
advent
of
cross-coupling
chemistry,
carbon
electrophiles
based
on
halides
or
pseudohalides
were
only
suitable
electrophilic
coupling
partners.
Almost
two
decades
passed
before
first
reaction
heteroatom-based
was
reported.
Early
work
by
Murai
and
Tanaka
initiated
investigations
into
silicon
electrophiles.
Narasaka
Johnson
pioneered
way
in
use
nitrogen
electrophiles,
while
Suginome
began
exploration
boron
The
chemistry
reviewed
within
provides
perspective
heteroatomic
specifically
silicon-,
nitrogen-,
boron-,
oxygen-,
phosphorus-based
transition-metal
catalyzed
cross-coupling.
For
purposes
this
review,
a
loose
definition
is
utilized;
all
reactions
minimally
proceed
via
an
oxidative
addition
event.
Although
not
traditional
sense,
we
have
also
included
that
join
electrophile
with
situ
generated
nucleophile.
However,
for
brevity,
those
involving
hydroamination
C–H
activation
as
key
step
are
largely
excluded.
This
includes
primary
references
published
up
to
including
October
2018.
Chemistry - A European Journal,
Journal Year:
2016,
Volume and Issue:
22(17), P. 5822 - 5829
Published: Feb. 16, 2016
Abstract
An
emerging
area
of
homogeneous
catalysis
is
the
use
catalysts
featuring
two
closely
associated
metal
sites.
This
approach
complements
traditional
focus
on
single‐site
and
makes
available
new
parameters
with
which
to
optimize
catalytic
behavior.
Single‐site
are
optimized
through
changing
1)
identity
metal,
2)
steric
electronic
properties
ligands.
Bimetallic
introduce
optimization
such
as
3)
catalyst
nuclearity
(mononuclear
vs.
binuclear),
4)
bimetallic
pairing
(relative
compatibility
sites).
In
order
harness
these
in
developing
systems,
it
necessary
first
understand
origin
selectivity
effects
that
already
have
been
documented.
Concept
article
highlights
chemo‐,
regio‐,
stereoselectivity
transformations,
using
selected
case
studies
from
recent
literature
illustrative
examples.
Reaction Chemistry & Engineering,
Journal Year:
2016,
Volume and Issue:
1(6), P. 658 - 666
Published: Jan. 1, 2016
An
automated,
droplet-flow
microfluidic
system
explores
and
optimizes
Pd-catalyzed
Suzuki-Miyaura
cross-coupling
reactions.
A
smart
optimal
DoE-based
algorithm
is
implemented
to
increase
the
turnover
number
yield
of
catalytic
considering
both
discrete
variables-palladacycle
ligand-and
continuous
variables-temperature,
time,
loading-simultaneously.
The
use
feedback
allows
for
experiments
be
run
with
catalysts
under
conditions
more
likely
produce
an
optimum;
consequently
complex
reaction
optimizations
are
completed
within
96
experiments.
Response
surfaces
predicting
performance
near
optima
generated
validated.
From
screening
results,
shared
attributes
successful
precatalysts
identified,
leading
improved
understanding
influence
ligand
selection
upon
transmetalation
oxidative
addition
in
mechanism.
Dialkylbiarylphosphine,
trialkylphosphine,
bidentate
ligands
assessed.
Chemistry - A European Journal,
Journal Year:
2021,
Volume and Issue:
27(54), P. 13481 - 13493
Published: July 16, 2021
The
story
of
C-C
bond
formation
includes
several
reactions,
and
surely
Suzuki-Miyaura
is
among
the
most
outstanding
ones.
Herein,
a
brief
historical
overview
insights
regarding
reaction
mechanism
provided.
In
particular,
catalytically
active
species
probably
main
concern,
thus
preactivation
in
competition
with,
or
even
assumes
role
rate
determining
step
(rds)
overall
reaction.
Computational
chemistry
key
identifying
rds
leading
to
milder
conditions
on
an
experimental
level
by
means
predictive
catalysis.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(2), P. 1180 - 1200
Published: Jan. 5, 2022
Key
similarities
and
differences
of
Pd
Ni
in
catalytic
systems
are
discussed.
Overall,
catalyze
a
vast
number
similar
C–C
C–heteroatom
bond-forming
reactions.
However,
the
smaller
atomic
radius
lower
electronegativity
Ni,
as
well
more
negative
redox
potentials
low-valent
species,
often
provide
higher
reactivity
oxidative
addition
or
insertion
reactions
persistence
alkyl-Ni
intermediates
against
β-hydrogen
elimination,
thus
enabling
activation
reluctant
electrophiles,
including
alkyl
electrophiles.
Another
key
point
relates
to
stability
open-shell
electronic
configurations
Ni(I)
Ni(III)
compared
with
Pd(I)
Pd(III).
Nickel
very
involve
interconvertible
Ni(n+)
active
species
variable
oxidation
states
(Ni(0),
Ni(I),
Ni(II),
Ni(III)).
In
contrast,
involving
Pd(III)
still
relatively
less
developed
may
require
facilitation
by
special
ligands
merging
photo-
electrocatalysis.
high
Pd(n+)
ensure
their
facile
reduction
Pd(0)
under
assistance
numerous
reagents
solvents,
providing
concentrations
molecular
Pd1(0)
complexes
that
can
reversibly
aggregate
into
Pdn
clusters
nanoparticles
form
cocktail
Pdn(0)
various
nuclearities
(i.e.,
values
"n").
Ni(0)
strong
reductants;
they
sensitive
deactivation
air
other
oxidizers
and,
consequence,
operate
at
catalyst
loadings
than
palladium
same
The
ease
robustness
versatility
for
catalysis,
whereas
variety
enables
diverse
uncommon
reactivity,
albeit
requiring
efforts
stabilization
nickel
systems.
As
discussion,
we
note
easily
"cocktail
particles"
different
but
(Pd1,
Pdn,
NPs),
behave
species"
is
stable
nuclearities.
Undoubtedly,
there
stronger
demand
ever
not
only
develop
improved
efficient
catalysts
also
understand
mechanisms
Chemical Science,
Journal Year:
2021,
Volume and Issue:
12(15), P. 5450 - 5457
Published: Jan. 1, 2021
This
works
demonstrates
the
implementation
of
an
electron
donor–acceptor
(EDA)
complex
platform
toward
Ni-catalyzed
C(sp3)–C(sp2)
bond
formation,
circumventing
need
for
exogenous
photocatalysts,
additives,
and
stoichiometric
metal
reductants.
