Organometallics,
Journal Year:
2024,
Volume and Issue:
43(21), P. 2707 - 2709
Published: Oct. 22, 2024
The
carbonylation
of
neutral
and
cationic
pyridine(diimine)
iron
neopentyl
complexes
was
studied.
While
the
addition
CO
to
(iPrPDI)FeCH2tBu
resulted
in
loss
alkyl
ligand
form
(iPrPDI)Fe(CO)2
free
pyridine(diimine),
variant
underwent
insertion
coordination
a
rare
example
low-spin
pyridine(diimine)iron(II)
organometallic
complex.
Prolonged
exposure
an
atmosphere
carbon
monoxide
migration
acyl
4-position
pyridine
tridentate
chelate.
Unprecedented
free
amine-oriented
regioselective
activations/carbonylations
mediated
by
hexacarbonylmolybdenum
have
been
developed
to
synthesize
5/6-membered
benzolactams
respectively.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(39)
Published: June 15, 2023
Abstract
This
report
describes
the
first
example
of
palladium‐catalyzed
carbonylative
difunctionalization
unactivated
alkenes
initiated
by
enolate
nucleophiles.
The
approach
involves
initiation
an
unstabilized
nucleophile
under
atmospheric
pressure
CO
and
termination
with
a
carbon
electrophile.
process
is
compatible
diverse
range
electrophiles,
including
aryl,
heteroaryl,
vinyl
iodides
to
yield
synthetically
useful
1,5‐diketone
products,
which
were
demonstrated
be
precursors
for
multi‐substituted
pyridines.
A
Pd
I
‐dimer
complex
two
bridging
units
was
observed
although
its
role
in
catalysis
not
yet
understood.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: May 31, 2024
Abstract
Although
dearomative
functionalizations
enable
the
direct
conversion
of
flat
aromatics
into
precious
three‐dimensional
architectures,
case
for
simple
arenes
remains
largely
underdeveloped
owing
to
high
aromatic
stabilization
energy.
We
herein
report
a
sequential
addition
two
nucleophiles
arene
π‐bonds
through
umpolung
chromium–arene
complexes.
This
mode
enables
divergent
carbonylation
reactions
benzene
derivatives
by
tolerating
various
in
combination
with
alcohols
or
amines
under
CO‐gas‐free
conditions,
thus
providing
modular
access
functionalized
esters
amides.
The
tunable
synthesis
1,3‐
1,4‐cyclohexadienes
as
well
construction
carbon
quaternary
centers
further
highlight
versatility
this
dearomatization.
Diverse
late‐stage
modifications
and
derivatizations
towards
synthetically
challenging
bioactive
molecules
reveal
synthetic
utility.
A
possible
mechanism
was
proposed
based
on
control
experiments
intermediate
tracking.
Organometallics,
Journal Year:
2024,
Volume and Issue:
43(21), P. 2707 - 2709
Published: Oct. 22, 2024
The
carbonylation
of
neutral
and
cationic
pyridine(diimine)
iron
neopentyl
complexes
was
studied.
While
the
addition
CO
to
(iPrPDI)FeCH2tBu
resulted
in
loss
alkyl
ligand
form
(iPrPDI)Fe(CO)2
free
pyridine(diimine),
variant
underwent
insertion
coordination
a
rare
example
low-spin
pyridine(diimine)iron(II)
organometallic
complex.
Prolonged
exposure
an
atmosphere
carbon
monoxide
migration
acyl
4-position
pyridine
tridentate
chelate.
