A
unique
family
of
N,N,π,C-palladacycles
are
synthesized
from
8-aminoquinoline-coupled
nopol
derivatives
through
directed
1,2-migratory
insertion
in
situ
generated
arylpalladium(II)
species
followed
by
β-carbon
elimination.
These
palladacycles
have
exceptional
stability
under
air
and
moisture
at
room
temperature,
enabling
successful
isola-tion
characterization
X-ray
crystallography,
NMR,
high-resolution
mass
spectrometry.
Computational
studies
shed
light
on
the
facile
β-alkyl
elimination
step
origins
high
these
post
β-carbon-elimination
complexes.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 10, 2025
Monoanionic,
bidentate-auxiliary-directed,
cobalt-catalyzed
C–H
bond
functionalization
has
become
a
very
useful
tool
in
organic
synthesis.
A
comprehensive
investigation
into
isolated
organometallic
intermediates
and
their
reactivity
within
the
catalytic
cycle
is
lacking.
We
report
here
mechanistic
studies
of
cobalt-catalyzed,
aminoquinoline-directed
C(sp2)–H
functionalization.
number
Co(III)
have
been
structurally
characterized,
including,
for
first
time
aminoquinoline
system,
complexes
arising
from
migratory
insertion
cobalt–carbon
bonds.
The
stoichiometric
reactions
cobalt(III)
aryls
with
alkenes,
alkynes,
carbon
monoxide,
cyclic
secondary
amines,
benzamides
explored.
oxidation
state
cobalt
product-forming
step
depends
on
nature
coupling
component.
Specifically,
annulation
alkynes
carbonylation
CO
likely
proceed
via
Co(I)/Co(III)
cycle.
Carbon–hydrogen
alkenes
as
well
benzamide
homocoupling,
(formally)
Co(IV)
species
involve
oxidatively
induced
reductive
elimination.
Organic Chemistry Frontiers,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
The
construction
of
new
C–C
bonds
via
inert
C(sp
3
)–H
bond
activation
has
garnered
significant
achievements
in
recent
decades,
particularly
with
palladacycles
serving
as
pivotal
intermediates.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(2), P. 882 - 886
Published: Jan. 4, 2024
In
this
work,
we
describe
the
unexpected
2-fold
Csp3–Csp3
bond
cleavage
suffered
by
cyclobutanols
in
presence
of
a
catalytic
amount
Pd(OAc)2
and
promoted
bulky
biaryl
JohnPhos
ligand.
Overall,
sequential
strained
an
unstrained
leads
to
formal
[2
+
2]-retrocyclization
products,
namely,
styrene
acetophenone
derivatives.
This
procedure
might
enable
use
as
masked
acetyl
groups,
resisting
harsh
conditions
organic
synthesis.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(13), P. 2523 - 2528
Published: March 27, 2024
A
migratory
insertion
of
carbenes
into
distal
γ-C(sp3)–H
bonds
aliphatic
amines
has
been
successfully
developed.
The
synergistic
interplay
among
a
palladium
catalyst,
picolinamide
directing
group,
carefully
selected
base
additive,
and
an
essential
ligand
proved
crucial
in
achieving
high
yields.
These
findings
hold
significant
value
for
advancing
the
exploration
regioselective
carbene
insertions
nonactivated
C(sp3)–H
bonds.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 14, 2024
A
solvent-controlled
Rh(III)-catalyzed
mono-
and
dual-C-H
bond
activation/carbene
migratory
insertion
with
diazo
compounds
as
a
single
coupling
partner
was
demonstrated.
The
reaction
proceeded
under
mild
conditions,
yielding
products
in
good
to
excellent
yields.
These
results
are
significant
for
the
development
of
domino
multiple
functionalization
C(sp
The Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
87(17), P. 11826 - 11837
Published: Aug. 24, 2022
A
visible-light-promoted
iodine-mediated
homo-coupling
of
diazo
was
first
described.
series
tetrasubstituted
olefins
were
synthesized
in
high
yields
and
with
low
to
Z-selectivities
from
phenyldiazoacetates.
For
3-diazooxindoles,
isoindigo
derivatives
provided
moderate
excellent
E-selectivities.
Experimental
results
showed
that
the
reaction
proceeded
through
a
diiodo
intermediate.
The
synthetic
usefulness
this
illustrated
by
synthesis
maleimide
dispiro
epoxy.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
42(2), P. 157 - 163
Published: Sept. 25, 2023
Comprehensive
Summary
Tetralin‐1‐carboxamides
are
frequently
incorporated
in
myriad
medicinally
important
molecules.
However,
their
existing
synthetic
routes
not
only
suffer
from
some
drawbacks
such
as
tedious
procedures,
harsh
reaction
conditions,
narrow
substrate
scope,
low
yields,
and
environmental
problems,
but
also
based
upon
the
elaboration
of
uneasily
available
non‐linear
tetralin
derivatives.
Herein,
we
describe
a
metal‐
additive‐free
visible
light‐induced
[4+2]
annulation
two
simple
linear
starting
materials,
namely
acrylamides
2‐benzyl‐2‐bromocarbonyls,
through
cascade
C(sp
3
)−Br/C(sp
2
)−H
bond
cleavage,
double
C−C
formation,
aromatization
sequence.
The
developed
protocol
provides
convenient,
efficient,
green
approach
to
variety
tetralin‐1‐carboxamide
derivatives
with
good
functional
group
compatibility.
Importantly,
resulting
products
could
undergo
LiCl‐mediated
mono‐decarboxylative
cyclization
process
further
furnish
architecturally
novel
bridged
polycyclic
imides
excellent
cis
‐diastereoselectivities.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
11(1), P. 176 - 182
Published: Nov. 21, 2023
Transition-metal
catalyzed
reactions
of
diazo
compounds
and
N
,
-dialkylnitrosoamines
had
been
developed,
leading
to
the
efficient
preparation
isoquinoline-1,3,4-trione
derivatives
or
nitroso
ylide
products
in
moderate
excellent
yields.
