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 Reviews,
Journal Year:
2016,
Volume and Issue:
116(19), P. 12564 - 12649
Published: Sept. 30, 2016
Pd-catalyzed
cross-coupling
reactions
that
form
C–N
bonds
have
become
useful
methods
to
synthesize
anilines
and
aniline
derivatives,
an
important
class
of
compounds
throughout
chemical
research.
A
key
factor
in
the
widespread
adoption
these
has
been
continued
development
reliable
versatile
catalysts
function
under
operationally
simple,
user-friendly
conditions.
This
review
provides
overview
N-arylation
found
both
basic
applied
research
from
2008
present.
Selected
examples
between
nine
classes
nitrogen-based
coupling
partners
(pseudo)aryl
halides
are
described
for
synthesis
heterocycles,
medicinally
relevant
compounds,
natural
products,
organic
materials,
catalysts.
Chemical Society Reviews,
Journal Year:
2018,
Volume and Issue:
47(15), P. 5786 - 5865
Published: Jan. 1, 2018
This
review
provides
an
overview
of
the
use
electrochemistry
as
appealing
platform
for
expediting
carbon–hydrogen
functionalization
and
carbon–nitrogen
bond
formation.
Angewandte Chemie International Edition,
Journal Year:
2017,
Volume and Issue:
56(51), P. 16136 - 16179
Published: May 23, 2017
Abstract
Metal‐catalyzed
cross‐coupling
reactions
belong
to
the
most
important
transformations
in
organic
synthesis.
Copper
catalysis
has
received
great
attention
owing
low
toxicity
and
cost
of
copper.
However,
traditional
Ullmann‐type
couplings
suffer
from
limited
substrate
scopes
harsh
reaction
conditions.
The
introduction
several
bidentate
ligands,
such
as
amino
acids,
diamines,
1,3‐diketones,
oxalic
diamides,
over
past
two
decades
totally
changed
this
situation
these
ligands
enable
copper‐catalyzed
coupling
aryl
halides
nucleophiles
at
both
temperatures
catalyst
loadings.
scope
also
been
greatly
expanded,
rendering
copper‐based
attractive
for
academia
industry.
In
Review,
we
have
summarized
latest
progress
development
useful
conditions
(hetero)aryl
with
different
nucleophiles.
Additionally,
recent
advances
boronates
trifluoromethylation
aromatic
electrophiles
will
be
discussed.
Science,
Journal Year:
2018,
Volume and Issue:
359(6374), P. 429 - 434
Published: Jan. 25, 2018
A
reaction
screen
in
flowing
solvent
Chemists
charged
with
manufacturing
pharmaceuticals
have
recently
been
exploring
the
efficiency
advantages
of
continuous
flow
techniques.
Perera
et
al.
now
show
that
a
apparatus
can
also
accelerate
optimization
earlier
drug
discovery
process.
They
modified
high-performance
liquid
chromatography
system
to
wide
variety
solvent,
ligand,
and
base
combinations
optimize
carbon-carbon
bond
formation.
Injecting
stock
solution
aliquots
catalyst
reactants
into
carrier
stream
let
authors
vary
main
efficiently
scale
up
optimal
conditions
for
product
isolation.
Science
,
this
issue
p.
429
Organometallics,
Journal Year:
2018,
Volume and Issue:
38(1), P. 3 - 35
Published: Nov. 27, 2018
Cross-coupling
reactions,
which
were
discovered
almost
50
years
ago,
are
widely
used
in
both
industry
and
academia.
Even
though
cross-coupling
reactions
now
represent
mature
technology,
there
is
still
a
significant
amount
of
research
this
area
that
aims
to
improve
the
scope
these
develop
more
efficient
catalysts,
make
practical.
In
tutorial,
brief
background
provided,
then
major
advances
over
last
20
described.
These
include
development
improved
ligands
precatalysts
for
extension
much
wider
range
electrophiles.
For
example,
common
with
sp3-hybridized
electrophiles
as
well
ester,
amide,
ether,
aziridine
substrates.
many
modern
substrates,
traditional
palladium-based
catalysts
less
than
systems
based
on
first-row
transition
metals
such
nickel.
Conventional
have
also
inspired
related
cross-electrophile
decarboxylative
couplings
metallaphotoredox
chemistry.
The
new
probably
at
same
stage
30
tutorial
highlights
how
strategies
may
be
applicable
making
Accounts of Chemical Research,
Journal Year:
2018,
Volume and Issue:
51(10), P. 2589 - 2599
Published: Sept. 21, 2018
Transition-metal-catalyzed
cross-coupling
reactions
represent
a
most
powerful
tool
for
the
rapid
construction
of
C-C
and
C-X
bonds
available
to
synthetic
chemists.
Recently,
tremendous
progress
has
been
made
in
burgeoning
area
amides
esters
enabled
by
regio-
chemoselective
acyl
(X
=
N,
O)
cleavage
using
well-defined
Pd(II)-NHC
complexes.
The
use
N-heterocyclic
carbenes
as
ligands
palladium-catalyzed
cross-couplings
permits
that
were
previously
impossible
palladium
or
could
be
achieved
only
under
harsh
conditions.
These
provide
an
attractive
method
chemists
manipulate
traditionally
inert
amide
ester
with
broad
generality
inherent
catalysis.
Research
stable
electrophiles
can
broadly
categorized
type
electrophile
undergoing
cross-coupling.
Recent
studies
have
shown
transition-metal
catalysis
represents
one
straightforward
wide-ranging
ways
manipulating
classically
into
generic
acyl-metal
intermediates
systematically
exploited
new
paradigm
organic
synthesis.
key
achieving
high
chemoselectivity
process
is
control
amidic
resonance
(nN
πC═O*
conjugation,
rotation
ca.
15-20
kcal/mol
planar
amides),
enabling
oxidative
addition
N-C
bond
metal
rational
predictable
manner.
This
mode
extended
C(acyl)-O
aryl
esters,
where
selective
C-O
accomplished
through
match
nucleophilic
catalysts.
two
types
transition-metal-catalyzed
concept
chemistry
because
ubiquity
precursors
Furthermore,
stability
provides
unprecedented
opportunities
orthogonal
strategies
presence
other
electrophiles.
In
this
Account,
we
highlight
advances
taken
place
past
few
years
field
focusing
on
both
(1)
stereoelectronic
properties
complexes
critical
realize
challenging
manifold
(2)
role
isomerization
barrier
broader
sense,
described
here
practical
approach
functionalize
common
functional
groups
synthesis
establishes
access
enable
nonconventional
strategies.
Journal of Agricultural and Food Chemistry,
Journal Year:
2018,
Volume and Issue:
66(34), P. 8914 - 8934
Published: July 31, 2018
Pd-catalyzed
cross-coupling
reactions
have
become
essential
tools
for
the
construction
of
carbon–carbon
and
carbon–heteroatom
bonds.
Over
last
three
decades,
great
efforts
been
made
with
chemistry
in
discovery,
development,
commercialization
innovative
new
pharmaceuticals
agrochemicals
(mainly
herbicides,
fungicides,
insecticides).
In
view
growing
interest
both
modern
crop
protection
chemistry,
this
review
gives
a
comprehensive
overview
successful
applications
various
methodologies,
which
implemented
as
key
steps
synthesis
(on
R&D
pilot-plant
scales)
such
Heck,
Suzuki,
Sonogashira,
Stille,
Negishi
reactions,
well
decarboxylative,
carbonylative,
α-arylative,
carbon–nitrogen
bond
bond-forming
reactions.
Some
perspectives
challenges
these
catalytic
coupling
processes
discovery
are
briefly
discussed
final
section.
The
examples
chosen
demonstrate
that
approaches
open-up
new,
low-cost,
more
efficient
industrial
routes
to
existing
agrochemicals,
methods
also
capability
lead
generation
pesticides
novel
modes
action
sustainable
protection.
