With
the
advent
of
high-throughput
methods
for
both
computation
and
experimentation,
data-rich
approaches
to
discovering
understanding
chemical
reactions
are
becoming
ever
more
central
catalysis
research.
Organopalladium
is
at
forefront
these
new
approaches,
providing
a
rich
proving
ground
method
development
validation.
This
critical
Perspective
discusses
number
recent
case
studies
from
academic
industrial
laboratories
that
illustrate
how
generate,
analyze,
correlate
large
data
sets
quantitative
predictions
reactivity
selectivity.
Both
power
potential
pitfalls
discussed,
as
opportunities
practical
fundamental
mechanistic
insights.
ACS Catalysis,
Год журнала:
2024,
Номер
14(9), С. 7127 - 7135
Опубликована: Апрель 23, 2024
We
describe
a
detailed
investigation
into
why
bulky
ligands-those
that
enable
catalysis
at
"12e
-"
Pd0-tend
to
promote
overfunctionalization
during
Pd-catalyzed
cross-couplings
of
dihalogenated
substrates.
After
one
cross-coupling
event
takes
place,
PdL
initially
remains
coordinated
the
π
system
nascent
product.
Selectivity
for
mono-
vs.
difunctionalization
arises
from
relative
rates
π-decomplexation
versus
second
oxidative
addition.
Under
Suzuki
coupling
conditions
in
this
work,
direct
dissociation
12e
-
π-complex
cannot
outcompete
Instead,
Pd
must
be
displaced
as
14e
PdL(L')
by
incoming
ligand
L'.
The
is
another
molecule
dichloroarene
if
reaction
do
not
include
π-coordinating
solvents
or
additives.
More
tends
result
when
increased
substrate
sterics
raises
energy
bimolecular
transition
state
separating
mono-cross-coupled
This
work
has
practical
implications
optimizing
selectivity
involving
multiple
halogens.
For
example,
we
demonstrate
small
coordinating
additives
like
DMSO
can
largely
suppress
and
precatalyst
structure
also
impact
selectivity.
Asian Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 14, 2025
Abstract
The
use
of
attractive
noncovalent
interactions
is
emerging
as
a
versatile
approach
to
address
site‐selectivity
challenges.
Herein,
we
report
ortho‐selective
Suzuki
coupling
reactions
in
water
2,3‐dichloroarenes
and
2,4‐dichloroarenes
bearing
hydroxy
group
the
presence
palladacycle
catalyst
directed
by
interactions.
Various
ortho‐substituted
arylphenols
arylbenzyl
alcohols
were
obtained
good
excellent
yields
with
high
selectivity.
Density
functional
theory
(DFT)
calculations
ab
initio
molecular
dynamics
(AIMD)
simulations
suggested
that
ortho
‐selective
dichlorophenols
dichlorobenzyl
occurred
through
electrostatic
hydrogen
bonding
interactions,
respectively.
Chemical Science,
Год журнала:
2023,
Номер
14(5), С. 1227 - 1233
Опубликована: Янв. 1, 2023
We
describe
unique
polyhalogenated
heteroarene
candidates
for
site-selective
cross-coupling,
which
shows
high
catalytic
performances
in
the
functionalization
of
polycyclic
metalla-aromatics
with
excellent
photophysical
properties.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Дек. 14, 2023
Controlling
site-selectivity
and
reactivity
in
chemical
reactions
continues
to
be
a
key
challenge
modern
synthetic
chemistry.
Here,
we
demonstrate
the
discovery
of
site-selective
on
water
surface
via
sequential
assembly
approach.
A
negatively
charged
surfactant
monolayer
guides
electrostatically
driven,
epitaxial,
aligned
reagent
amino-substituted
porphyrin
molecules,
resulting
well-defined
J-aggregated
structure.
This
constrained
geometry
molecules
prompts
subsequent
directional
alignment
perylenetetracarboxylic
dianhydride
reagent,
enabling
selective
formation
one-sided
imide
bond
between
reagent.
Surface-specific
in-situ
spectroscopies
reveal
underlying
mechanism
dynamic
interface
that
promotes
multilayer
growth
product.
The
reaction
is
further
demonstrated
by
three
reversible
irreversible
reactions,
such
as
imide-,
imine-,
1,
3-diazole
(imidazole)-
bonds
involving
molecules.
unique
approach
enables
can
bring
on-water
synthesis
forefront
organic
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(7), С. 965 - 970
Опубликована: Янв. 13, 2023
Abstract
A
synthesis
of
1,4‐diborylated
benzenes
was
achieved
by
the
Ru‐catalyzed
regioselective
co‐cyclotrimerization
alkynes
with
a
commercially
available
ethynyl
boronate.
The
reaction
is
applicable
to
wide
array
metal‐coordinating
groups,
providing
synthetically
useful
diborylated
in
23–68%
isolated
yields.
DFT
calculations
shed
light
on
course
and
origin
its
remarkable
regioselectivity.
Selected
were
converted
into
various
products,
such
as
quinones
hydroquinones,
including
three
natural
bioactive
small
molecules.
magnified
image
Organometallics,
Год журнала:
2023,
Номер
42(22), С. 3178 - 3191
Опубликована: Ноя. 6, 2023
A
detailed
computational
analysis
was
carried
out
using
density
functional
theory
(DFT)
calculations
to
investigate
the
reaction
between
arenediazonium
salts
and
Pd(0)
complexes
under
"ligand-less"
conditions.
In
present
study,
three
plausible
mechanisms
scenarios
were
revealed:
nucleophilic
substitution,
intramolecular
insertion,
a
multistep
1,3-palladium
migration.
The
oxidative
addition
of
palladium
aryldiazonium
cation
(ArN2+)
is
rapid
irreversible
reaction.
Additionally,
ArN2+
counterion
BF4–
does
not
have
significant
impact
on
free
energy
profile.
Based
DFT
calculations,
formation
aryl-palladium(II)
complex
identified
as
thermodynamic
driving
force,
regardless
investigated
mechanism.
migration
mechanism
preferred,
but
substitution
insertion
could
be
ruled
out.
According
natural
population
(NPA)
charges,
oxidation
takes
place
through
coordination
metal
specifically
for
mechanism,
in
contrast
aryl
halide
counterpart
systems,
which
occurs
transition-state
structures.
thermodynamics
affected
by
electronics
para-substituents
phenyl
ring
ArN2+.
However,
overall
barriers
are
less
substituents.
investigation
different
conditions
methanol
(MeOH),
N,N-dimethylformamide
(DMF),
acetonitrile
(MeCN)
solvents.
Specifically,
MeCN
solvent,
found
exothermic.
Taken
together,
strong
electron
acceptor
capacity
high
reactivity
provide
facile
strongly
positively
charged
atom
all
palladium-containing
intermediates
transition
states,
reflecting
low
exothermicity
revealed
at
room
temperature.
Furthermore,
current
study
suggests
that
palladium(II)
aryldiazenido
(int6a
or
int6b)
stable
intermediates,
indicating
them
promising
precursor
prospective
experimental
mechanistic
investigations.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(13), С. 9243 - 9254
Опубликована: Июнь 15, 2024
Chemoselective
amination
is
a
highly
desired
synthetic
methodology,
given
its
importance
as
possible
strategy
to
synthesize
various
drug
molecules
and
agrochemicals.
We,
herein,
disclose
chemoselective
Cu(II)-PTABS-promoted
of
pyrimidine
structural
feature
containing
different
halogen
atoms.
Chemical Communications,
Год журнала:
2023,
Номер
59(62), С. 9513 - 9516
Опубликована: Янв. 1, 2023
We
have
developed
an
effective
photochemical
method
for
site-selective
(hetero)arylation
of
polychlorinated
heteroarenes.
This
approach
eliminates
the
need
transition
metal
catalysts
and
photosensitizers
by
relying
on
in
situ
formation
unconventional
electron
donor-acceptor
(EDA)
complexes
between
two
substrates
a
basic
additive.
Our
protocol
yields
chlorine-containing
biaryl
heterocyclic
compounds
with
high
levels
site-selectivity,
which
are
significant
importance
both
synthetic
medicinal
chemistry.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(15), С. 11036 - 11044
Опубликована: Июль 24, 2023
Regioselective
amination
of
polyhalogenated
heteroarenes
(especially
pyrimidines)
has
extensive
synthetic
and
commercial
relevance
for
drug
synthesis
applications
but
is
plagued
by
the
lack
effective
strategies.
Herein,
we
report
Cu(II)/PTABS-promoted
highly
regioselective
nucleophilic
aromatic
substitution
(SNAr)
polychlorinated
pyrimidines
assisted
DFT
predictions
bond
dissociation
energies
different
C-Cl
bonds.
The
unique
reactivity
Cu(II)-PTABS
been
attributed
to
coordination/activation
mechanism
that
known
operate
in
these
reactions,
further
insights
into
catalytic
species
have
also
provided.
