Molecules,
Journal Year:
2023,
Volume and Issue:
28(6), P. 2729 - 2729
Published: March 17, 2023
Ferrocenium
catalysis
is
a
vibrant
research
area,
and
an
increasing
number
of
ferrocenium-catalyzed
processes
have
been
reported
in
the
recent
years.
However,
ferrocenium
cation
not
very
stable
solution,
which
may
potentially
hamper
catalytic
applications.
In
effort
to
stabilize
ferrocenium-type
architectures
by
inserting
bridge
between
cyclopentadienyl
rings,
we
investigated
two
ferrocenophanium
(or
ansa-ferrocenium)
cations
with
respect
their
stability
activity
propargylic
substitution
reactions.
One
complexes
was
characterized
single
crystal
X-ray
diffraction.
Cyclic
voltammetry
experiments
ferrocenophane
parent
compounds
were
performed
absence
presence
alcohol
nucleophiles,
solution
judged
based
on
reversibility
electron
transfer.
The
revealed
moderate
stabilizing
effect
bridge,
albeit
pronounced
or
straightforward.
Catalytic
test
reactions
decreased
compared
cation.
It
appears
that
somewhat
stabilized
show
activity.
Trends in Chemistry,
Journal Year:
2023,
Volume and Issue:
5(3), P. 174 - 200
Published: Feb. 14, 2023
Organic
peroxides
are
becoming
popular
intermediates
for
novel
chemical
transformations.
The
weak
O-O
bond
is
readily
reduced
by
transition
metals,
including
iron
and
copper,
to
initiate
a
radical
cascade
process
that
breaks
C-C
bonds.
Great
potential
exists
the
rapid
generation
of
complexity,
originating
from
ability
couple
resulting
free
radicals
with
wide
range
partners.
First,
this
review
article
discusses
history
synthesis
organic
peroxides,
providing
context
necessary
understand
methodology.
Then,
it
highlights
91
examples
recent
applications
functionalization
bonds
accessed
through
metal-mediated
reduction
peroxides.
Finally,
we
provide
some
comments
about
safety
when
working
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(13), P. 4757 - 4762
Published: Jan. 1, 2024
α-Keto-,
β-acetoxy-
and
β-amidoalkylsilyl
peroxides
are
prepared
from
various
precursors
utilized
for
Fe-catalyzed
visible-light-promoted
radical
functionalization
with
coupling
partners
under
mild
conditions
a
broad
substrate
scope.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(88), P. 13175 - 13178
Published: Jan. 1, 2023
An
NHC
organocatalytic
radical
acylation
of
cycloalkyl
silyl
peroxides
with
aldehydes
was
developed
for
the
efficient
and
rapid
synthesis
long-chain
1,6-/1,7-/1,8-diketones,
especially
unsymmetrical
ones.
ChemCatChem,
Journal Year:
2023,
Volume and Issue:
15(23)
Published: Oct. 17, 2023
Abstract
Transition‐metal‐catalyzed
radical
relay
cross‐coupling
reactions
of
1,3‐dienes
have
recently
emerged
as
one
the
most
powerful
methods
for
construction
structurally
diverse
allylic
compound
in
a
single
chemical
step.
However,
there
still
has
been
limited
success
expanding
substrate
scope
precursors
and
coupling
partners,
well
exploring
catalytic
asymmetric
variants.
Herein,
we
report
copper‐catalyzed
enantioselective
three‐component
1,2‐alkylesterification
using
cycloalkyl
hydroperoxides
carbonyl‐containing
alkyl
sources
carboxylic
acids
O‐nucleophiles
under
mild
redox‐neutral
conditions.
This
protocol
features
broad
good
functional
group
tolerance
with
respect
to
each
component,
providing
practical
access
variety
distally
keto‐functionalized
esters
high
enantioselectivity.
Mechanistic
studies
suggest
involvement
sequential
C−O
this
reaction.
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(12), P. 2370 - 2374
Published: Jan. 1, 2024
An
efficient
method
was
developed
for
the
one-pot
construction
of
pyrrolo[1,2-
a
]quinoxalines
via
Cu(
ii
)-catalyzed
domino
reaction
between
2-(1
H
-pyrrol-1-yl)anilines
and
alkylsilyl
peroxides.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 27, 2024
The
selective
reaction
of
cyclic
aminoperoxides
with
FeCl2
proceeds
through
a
sequence
O–O
and
C–C
bond
cleavages,
followed
by
intramolecular
cyclization,
yielding
functionalized
tetrahydrofurans
in
44–82%
yields.
Replacing
the
peroxyacetal
group
peroxide
structure
peroxyaminal
fragment
fundamentally
alters
pathway.
Instead
producing
linear
ketones,
this
modification
leads
to
formation
hard-to-access
substituted
tetrahydrofurans.
Although
aminoperoxide
cores
undergo
multiple
scissions,
cascade
is
atom-economical.
Computational
analysis
shows
that
O-ligands
at
Fe
center
have
enough
radical
character
promote
fragmentation
subsequent
cyclization.
stereoelectronic
flexibility
oxygen,
combined
iron's
capacity
stabilize
reactive
intermediates
during
multistep
cascade,
explains
efficiency
new
atom-economic
rearrangement.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(17), P. 2958 - 2963
Published: March 23, 2023
Alkyl
tert-butyl
peroxides
are
prepared
from
the
corresponding
tert-alkyl
precursors
and
hydroperoxide
in
presence
of
a
promoter.
These
substrates
can
be
utilized
mild
copper-catalyzed
radical
functionalization
that
utilizes
several
coupling
partners
has
broad
substrate
scope.
A
mechanistic
study
suggests
alkyl
species
participate
reactions.
