Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(45), P. 9659 - 9664
Published: Oct. 31, 2024
1,3-Difunctionalization
of
donor–acceptor
cyclopropanes
with
copper
nitrate
and
N-halosuccinimide
was
developed
to
efficiently
afford
γ-halonitrates.
The
pivotal
factor
this
protocol
lies
in
the
dual
role
as
a
Lewis
acid
an
ideal
nitrooxy
source.
given
approach
features
easy
handling,
good
functional
group
compatibility,
wide
substrate
scope.
Furthermore,
various
transformations
obtained
γ-chloronitrates
underscore
remarkable
synthetic
potential
inherent
method.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(27), P. 5856 - 5861
Published: July 1, 2024
Here,
we
present
a
silver-catalyzed
decarboxylative
nitrooxylation
via
radical-based
approach.
The
substrate
scope
of
this
reaction
prototype
extends
to
nonactivated
primary
and
secondary
carboxylic
acids.
This
protocol
provides
practical
method
for
the
synthesis
an
unprecedented
family
organic
nitrates
exhibits
wide
functional
group
compatibility.
Preliminary
mechanistic
studies
reveal
that
high-valent
silver(II)
nitrate
complex
is
versatile
NO
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(40)
Published: July 10, 2024
Abstract
Nitrate
esters
hold
pivotal
roles
in
pharmaceuticals,
energetic
materials,
and
atmospheric
processes,
motivating
the
development
of
efficient
synthesis
routes.
Here,
we
present
a
novel
catalytic
method
for
nitrates
via
direct
O
‐nitration
alcohols,
addressing
limitations
current
traditional
methods.
Leveraging
bench‐stable
recoverable
N
,6‐dinitrosaccharin
reagent,
our
strategy
employs
magnesium
triflate
to
achieve
mild
selective
offering
broad
substrate
scope
unprecedentedly
large
functional
group
tolerance
(e.g.
alkenes,
alkynes,
carbonyls).
DFT
mechanistic
studies
reveal
dual
role
catalyst
activation
both
nitrating
reagent
alcohol
substrate.
They
also
unveil
barrierless
proton
transfer
upon
formation
widely‐accepted
–
yet
elusive
solution
nitrooxonium
ion
intermediate.
Overall,
work
contributes
mild,
selective,
sustainable
approaches
synthesis,
with
potential
applications
drug
discovery,
materials
science,
environmental
chemistry.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(45), P. 9659 - 9664
Published: Oct. 31, 2024
1,3-Difunctionalization
of
donor–acceptor
cyclopropanes
with
copper
nitrate
and
N-halosuccinimide
was
developed
to
efficiently
afford
γ-halonitrates.
The
pivotal
factor
this
protocol
lies
in
the
dual
role
as
a
Lewis
acid
an
ideal
nitrooxy
source.
given
approach
features
easy
handling,
good
functional
group
compatibility,
wide
substrate
scope.
Furthermore,
various
transformations
obtained
γ-chloronitrates
underscore
remarkable
synthetic
potential
inherent
method.
