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.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(49)
Published: Aug. 22, 2023
Abstract
Much
progress
has
been
made
in
the
development
of
methods
to
both
create
compounds
that
contain
C−F
bonds
and
functionalize
bonds.
As
such,
are
becoming
common
versatile
synthetic
functional
handles.
This
review
summarizes
advantages
defluorinative
functionalization
reactions
for
small
molecule
synthesis.
The
coverage
is
organized
by
type
carbon
framework
fluorine
attached
mono‐
polyfluorinated
motifs.
main
challenges,
opportunities
advances
discussed
each
class
organofluorine.
Most
text
focuses
on
case
studies
illustrate
how
defluorofunctionalization
can
improve
routes
targets
or
properties
enable
unique
mechanisms
reactions.
broader
goal
showcase
incorporating
exploiting
design
routes,
improvement
specific
advent
new
methods.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(23), P. 15850 - 15859
Published: May 28, 2024
Light-driven
strategies
that
enable
the
chemoselective
activation
of
a
specific
bond
in
multifunctional
systems
are
comparatively
underexplored
comparison
to
transition-metal-based
technologies,
yet
desirable
when
considering
controlled
exploration
chemical
space.
With
current
drive
discover
next-generation
therapeutics,
reaction
design
enables
strategic
incorporation
an
sp3
carbon
center,
containing
multiple
synthetic
handles
for
subsequent
space
would
be
highly
enabling.
Here,
we
describe
photoactivation
ambiphilic
C1
units
generate
α-bimetalloid
radicals
using
only
Lewis
base
and
light
source
directly
activate
C–I
bond.
Interception
these
transient
with
various
SOMOphiles
rapid
synthesis
organic
scaffolds
(B,
Si,
Ge)
orthogonal
activation.
In-depth
theoretical
mechanistic
studies
reveal
prominent
role
2,6-lutidine
forming
photoactive
charge
transfer
complex
stabilizing
situ
generated
iodine
radicals,
as
well
influential
boron
p-orbital
activation/weakening
This
simple
efficient
methodology
enabled
expedient
access
functionalized
3D
frameworks
can
further
derivatized
available
technologies
C–B
C–Si
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(28), P. 19249 - 19260
Published: July 3, 2024
Two
limiting
mechanisms
are
possible
for
oxidative
addition
of
(hetero)aryl
(pseudo)halides
at
Pd(0):
a
3-centered
concerted
and
nucleophilic
displacement
mechanism.
Until
now,
there
has
been
little
understanding
about
when
each
mechanism
is
relevant.
Prior
investigations
to
distinguish
between
these
pathways
were
limited
few
specific
combinations
the
substrate
ligand.
Here,
we
computationally
evaluated
over
180
transition
structures
in
order
determine
mechanistic
trends
based
on
substrate,
ligand(s),
coordination
number.
Natural
abundance
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(5), P. 3278 - 3286
Published: Feb. 15, 2024
Herein,
we
reported
the
enantioconvergent
Csp3–Csp2
cross-coupling
reaction
with
1,4-dihydropyridine
(DHP)
derivatives
via
photoredox/nickel
dual
catalysis
to
access
chiral
products
good
yield
and
enantioselectivity.
The
operationally
simple
was
carried
out
under
mild
conditions
functional
group
tolerance.
Due
use
of
a
stoichiometric
equivalent
aryl/alkenyl
halides
as
coupling
partners,
sequential
iterative
synthesis
could
be
achieved
smoothly
in
one
pot
for
position
isomers
stereoisomers.
In
proposed
mechanism,
kinetic
experiments
mechanistic
studies
indicated
that
radical
generation,
depended
on
excited
photocatalyst
DHP,
rate-determining
step.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 19, 2025
Under
most
conditions,
2,4-dihalopyrimidines
undergo
substitution
reactions
at
C4.
Here
we
report
that
Pd(II)
precatalysts
supported
by
bulky
N-heterocyclic
carbene
ligands
uniquely
effect
C2-selective
cross-coupling
of
2,4-dichloropyrimidine
with
thiols.
The
regioselectivity
this
reaction
stands
in
stark
contrast
to
∼1500
previously
reported
Pd-catalyzed
cross-couplings
favor
C4
the
absence
other
substituents
on
pyrimidine
ring.
Selectivity
catalytic
system
herein
is
extremely
sensitive
structure
precatalyst,
largely
due
competing
C4-selective
nucleophilic
aromatic
substitution.
C2-selectivity
high
1°
thiols
and
thiophenols,
a
range
substituted
dichloropyrimidines
can
be
used.
atypical
selectivity
transformation
may
facilitate
diversity-oriented
synthesis,
as
demonstrated
for
derivatives
an
antiviral
agent.
these
C2─Cl
cleavage
not
take
place
through
typical
oxidative
addition
pathway.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(21), P. 11781 - 11788
Published: May 19, 2023
Dihydropyridines
are
versatile
building
blocks
for
the
synthesis
of
pyridines,
tetrahydropyridines,
and
piperidines.
Addition
nucleophiles
to
activated
pyridinium
salts
allows
1,2-,
1,4-,
or
1,6-dihydropyridines;
however,
this
process
often
leads
a
mixture
constitutional
isomers.
Catalyst-controlled
regioselective
addition
pyridiniums
has
potential
solve
problem.
Herein,
we
report
that
boron-based
can
be
accomplished
by
choice
Rh
catalyst.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(17), P. 4408 - 4436
Published: Jan. 1, 2023
This
article
presents
a
comprehensive
analysis
of
the
progress
in
palladium-catalyzed
coupling
reactions,
with
an
emphasis
on
how
ligand
characteristics
affect
chemoselectivity
aryl
(pseudo)halides.
Asian Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 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.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
90(5), P. 1895 - 1904
Published: Jan. 24, 2025
Multipalladium
clusters
possess
peculiar
structures
and
synergistic
effects
for
reactivity
selectivity.
Herein,
C3-symmetric
tripalladium
(1,
0.5
mol
%)
afford
C2-regioselective
SMCC
of
2,4-dibromopyridine
with
phenylboronic
acids
or
pinacol
esters
(C2:C4
up
to
98:1),
in
contrast
Pd(OAc)2
ligand-free
conditions.
In
addition,
similar
C2-selectivity
was
achieved
Sonogashira,
Negishi,
Kumada
coupling
reactions.
This
method
highlights
their
powerful
catalytic
ability,
exclusive
C2-selectivity,
broad
substrate
scope,
efficient
amplification,
multiple
ligand-exchange
feasibility
demonstrates
that
the
conventional
sites
could
be
successfully
regulated
even
reversed
by
catalysts.
