Organic Process Research & Development,
Journal Year:
2019,
Volume and Issue:
23(8), P. 1594 - 1601
Published: July 26, 2019
Recent
advances
in
Pd-catalyzed
carbon–nitrogen
cross-coupling
have
enabled
the
use
of
soluble
organic
bases
instead
insoluble
or
strong
inorganic
that
are
traditionally
employed.
The
single-phase
nature
these
reaction
conditions
facilitates
their
implementation
continuous
flow
systems,
high-throughput
optimization
platforms,
and
large-scale
applications.
In
this
work,
we
utilized
an
automated
microfluidic
platform
to
determine
optimal
for
couplings
aryl
triflate
with
four
types
commonly
employed
amine
nucleophiles:
anilines,
amides,
primary
aliphatic
amines,
secondary
amines.
By
analyzing
trends
catalyst
reactivity
across
different
temperatures,
base
strengths,
concentrations,
developed
a
set
general
recommendations
reactions
involving
bases.
algorithm
determined
supported
by
dialkyltriarylmonophosphine
ligand
AlPhos
was
most
active
coupling
each
nucleophile.
Furthermore,
our
revealed
phosphazene
BTTP
can
be
used
facilitate
alkylamines
triflates.
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.
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
Journal of the American Chemical Society,
Journal Year:
2015,
Volume and Issue:
137(6), P. 2195 - 2198
Published: Feb. 4, 2015
Single-electron-mediated
alkyl
transfer
affords
a
novel
mechanism
for
transmetalation,
enabling
cross-coupling
under
mild
conditions.
Here,
general
conditions
are
reported
of
secondary
alkyltrifluoroborates
with
an
array
aryl
bromides
mediated
by
Ir
photoredox
catalyst
and
Ni
catalyst.
Science,
Journal Year:
2020,
Volume and Issue:
369(6501), P. 310 - 315
Published: July 17, 2020
Separating
organics
without
distillation
Hydrocarbon
is
a
widespread
and
energy-intensive
process.
Membranes
might
offer
an
alternative
approach,
but
few
can
survive
immersion
in
organic
solvents
nor
are
they
able
to
extract
relatively
small
molecules.
Thompson
et
al.
developed
series
of
polymers
intrinsic
microporosity
that
used
for
membrane-based
separations
compounds
solvent
(see
the
Perspective
by
Brennecke
Freeman).
The
new
membrane
has
molecular
weight
cutoff
253
daltons,
far
lower
than
existing
ones
closer
600
daltons.
were
separate
light
shale
crude
oil
succeeded
fractionation
weights
about
170
Science
this
issue
p.
310
;
see
also
254
Science,
Journal Year:
2018,
Volume and Issue:
362(6415), P. 670 - 674
Published: Sept. 20, 2018
Despite
the
enormous
potential
for
use
of
stereospecific
cross-coupling
reactions
to
rationally
manipulate
three-dimensional
structure
organic
molecules,
factors
that
control
transfer
stereochemistry
in
these
remain
poorly
understood.
Here
we
report
a
mechanistic
and
synthetic
investigation
into
enantioenriched
alkylboron
nucleophiles
Pd-catalyzed
Suzuki
reactions.
By
developing
suite
molecular
descriptors
phosphine
ligands,
could
apply
predictive
statistical
models
select
or
design
distinct
ligands
respectively
promoted
stereoinvertive
stereoretentive
Stereodefined
branched
structures
were
thereby
accessed
through
predictable
manipulation
absolute
stereochemistry,
general
model
mechanism
transmetallation
was
proposed.
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.
