Chemistry Letters,
Journal Year:
2023,
Volume and Issue:
52(10), P. 783 - 787
Published: Aug. 31, 2023
Abstract
A
palladium-catalyzed
method
was
developed
for
the
synthesis
of
β-enaminones
from
saturated
ketones
using
allyl
acetate.
In
this
reaction,
acetate
acts
as
a
hydrogen
scavenger
to
α,β-dehydrogenate
in
presence
palladium
catalyst
and
diamine
ligand.
This
reaction
achieved
internal
β-carbon–nitrogen
bond
formation
first
time
via
dehydrogenation/conjugate
addition
protocol,
eliminating
need
isolate
unstable
α,β-unsaturated
generated
reaction.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(20)
Published: March 4, 2024
Abstract
Dienes
have
been
of
great
interest
to
synthetic
chemists
as
valuable
substrates
due
their
abundance
and
ease
synthesis.
Their
unique
stereoelectronic
properties
enable
broad
reactivity
with
a
wide
range
transition
metals
construct
molecular
complexity
facilitating
synthesis
biologically
active
compounds.
In
addition,
structural
diene
variation
can
result
in
substrate‐controlled
reactions,
providing
mechanistic
insights
into
selectivity
patterns.
The
last
decade
has
seen
wealth
new
methodologies
involving
through
the
power
metal
catalysis.
This
review
summarizes
recent
advances
remaining
opportunities
for
metal‐catalyzed
transformations
dienes.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(7), P. 4985 - 4992
Published: Feb. 6, 2024
Unsaturated
amides
represent
common
functional
groups
found
in
natural
products
and
bioactive
molecules
serve
as
versatile
synthetic
building
blocks.
Here,
we
report
an
iron(II)/cobalt(II)
dual
catalytic
system
for
the
syntheses
of
distally
unsaturated
amide
derivatives.
The
transformation
proceeds
through
iron
nitrenoid-mediated
1,5-hydrogen
atom
transfer
(1,5-HAT)
mechanism.
Subsequently,
radical
intermediate
undergoes
hydrogen
abstraction
from
vicinal
methylene
by
a
cobaloxime
catalyst,
efficiently
yielding
β,γ-
or
γ,δ-unsaturated
derivatives
under
mild
conditions.
efficiency
Co-mediated
HAT
can
be
tuned
varying
different
auxiliaries,
highlighting
generality
this
protocol.
Remarkably,
desaturation
protocol
is
also
amenable
to
practical
scalability,
enabling
synthesis
carbamates
ureas,
which
readily
converted
into
various
valuable
molecules.
Advanced Materials,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 18, 2024
Abstract
For
traditional
metal
complexes,
intricate
chemistry
is
required
to
acquire
appropriate
ligands
for
controlling
the
electron
and
steric
hindrance
of
active
centers.
Comparatively,
preparation
single‐atom
catalysts
much
easier
with
more
straightforward
effective
accesses
arrangement
control
The
presence
coordination
atoms
or
neighboring
functional
on
supports'
surface
ensures
stability
single‐atoms
their
interactions
individual
substantially
regulate
performance
Therefore,
collaborative
interaction
between
surrounding
environment
enhances
initiation
reaction
substrates
formation
transformation
crucial
intermediate
compounds,
which
imparts
significant
catalytic
efficacy,
rendering
them
a
valuable
framework
investigating
correlation
structure
activity,
as
well
mechanism
in
organic
reactions.
Herein,
comprehensive
overviews
both
homogeneous
complexes
reactions
are
provided.
Additionally,
reflective
conjectures
about
advancement
synthesis
also
proposed
present
reference
later
development.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 11, 2025
Herein,
we
report
that
binuclear
copper
complexes
used
as
dehydrogenative
catalysts,
combined
with
oxygen
an
oxidant
and
2,2,6,6-tetramethylpiperidinyl-1-oxide
(TEMPO)
additive,
are
capable
of
effectively
catalyzing
the
successive
dehydrogenation
aromatic
propanols
to
produce
α,β-unsaturated
aldehydes.
This
method
has
advantages
high
efficiency,
simple
operation,
oxidant.
The
reaction
mechanism
continuous
was
investigated
by
in
situ
infrared
spectroscopy
control
experiments.
process
suggested
phenylpropanol
first
oxidized
arylpropanals
then
underwent
α,β-selective
carbonyl
group
yield
protocol
provides
insights
into
design
synthesis
efficient
catalysts
for
preparation
aldehydes
propanols.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(71)
Published: Oct. 17, 2023
Abstract
This
review
comprehensively
analyses
representative
examples
of
Pd(II)‐catalyzed
late‐stage
C−H
activation
reactions
and
demonstrates
their
efficacy
in
converting
bonds
at
multiple
positions
within
drug
(derivative)
molecules
into
diverse
functional
groups.
These
transformative
hold
immense
potential
medicinal
chemistry,
enabling
the
efficient
selective
functionalization
specific
sites
molecules,
thereby
enhancing
pharmacological
activity
expanding
scope
candidates.
Although
notable
articles
have
focused
on
drug‐like
using
transition‐metal
catalysts,
reviews
specifically
focusing
Pd(II)
catalysts
are
required
owing
to
prominence
as
most
widely
utilized
metal
for
ability
introduce
a
myriad
groups
bonds.
The
utilization
Pd‐catalyzed
methodologies
impressive
success
introducing
various
groups,
such
cyano
(CN),
fluorine
(F),
chlorine
(Cl),
aromatic
rings,
olefin,
alkyl,
alkyne,
hydroxyl
with
high
regioselectivity
functional‐group
tolerance.
breakthroughs
serve
invaluable
tools
discovery
development,
offering
strategic
options
optimize
candidates
drive
exploration
innovative
therapeutic
solutions.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(7), P. 4795 - 4802
Published: Feb. 8, 2024
An
iron/chromium
system
(Fe(OAc)2,
CpCr(CO)3H)
catalyzes
the
preparation
of
β,γ-
or
γ,δ-unsaturated
amides
from
1,4,2-dioxazol-5-ones.
acyl
nitrenoid
iron
complex
seems
likely
to
be
responsible
for
C–H
activation.
A
cascade
three
H•
transfer
steps
appears
involved:
(i)
abstraction
a
remote
bond
by
N,
(ii)
Cr
and
(iii)
radical
substituent
Cr•.
The
observed
kinetic
isotope
effects
are
consistent
with
proposed
mechanism
if
formation
is
rate-determining
step.
Fe/Cr
catalysts
can
also
desaturate
substituted
1,4,2-dioxazol-5-ones
3,5-dienamides.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 18, 2025
Herein,
(E,E)-1,5-diamino-1,3-dienes
are
stereoselectively
synthesized
from
substituted
aryl
derivatives
via
a
rhodium(II)-catalyzed
C(sp3)-H
functionalization
involving
cascade
of
cyclopropane
ring
expansion,
cyclobutene
formation,
to
1,3-diene
conversion,
and
regioselective
diamination.
Mechanistic
studies
show
this
one-pot
process
proceeds
through
hydrogen
atom
transfer
(HAT),
radical-polar
crossover
(RPC),
elimination,
electrocyclic
ring-opening,
radical
addition,
underscoring
rhodium(II)'s
role
in
radical-mediated
catalysis
beyond
traditional
rhodium(II)
nitrenoid
chemistry.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(16)
Published: March 22, 2024
Abstract
A
method
for
the
selective
dimerization
of
styrenes
and
acrylates
has
been
developed.
The
reaction
is
catalyzed
by
a
very
low
amount
palladium
acetate
in
molten
tetrabutylammonium
without
need
any
additional
ligand.
use
this
enabled
coupling
substituted
vinyl
arenes
reasonable
yields
to
give
exclusively
(E,E)‐1,4‐diarylbutadiene
motif
within
7–10
h.
Acrylates,
on
other
hand,
exhibit
higher
reactivity,
dibutyl
acrylate
resulted
quantitative
synthesis
2‐methyleneglutarate
less
than
2
This
selectivity
unprecedented
literature.
role
ionic
liquid
different
catalytic
pathways
involved
two
processes
were
also
elucidated.
