Herein,
we
reported
an
efficient
and
straightforward
desaturative
β-C(sp3)-H
sulfonylation
phosphonylation
of
cyclic
amines
driven
by
electrochemistry
using
catalytic
amounts
Cp2Fe
as
the
redox
mediator.
This
protocol
which
had
good
functional
group
compatibility,
provided
desired
enaminyl
sulfone
phosphine
oxide
products
with
high
chemo-
regio-selectivity
under
mild
conditions.
Preliminary
mechanistic
study
indicated
that
underwent
multiple
single-electron
oxidation
deprotonation
process,
then
was
captured
sulfonyl
radical
or
phosphonyl
to
deliver
products.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(16), P. 10302 - 10380
Published: Aug. 14, 2023
Nitroxides,
also
known
as
nitroxyl
radicals,
are
long-lived
or
stable
radicals
with
the
general
structure
R1R2N–O•.
The
spin
distribution
over
nitroxide
N
and
O
atoms
contributes
to
thermodynamic
stability
of
these
radicals.
presence
bulky
N-substituents
R1
R2
prevents
radical
dimerization,
ensuring
their
kinetic
stability.
Despite
reactivity
toward
various
transient
C
some
nitroxides
can
be
easily
stored
under
air
at
room
temperature.
Furthermore,
oxidized
oxoammonium
salts
(R1R2N═O+)
reduced
anions
(R1R2N–O–),
enabling
them
act
valuable
oxidants
reductants
depending
on
oxidation
state.
Therefore,
they
exhibit
interesting
across
all
three
states.
Due
fascinating
properties,
find
extensive
applications
in
diverse
fields
such
biochemistry,
medicinal
chemistry,
materials
science,
organic
synthesis.
This
review
focuses
versatile
For
use
other
important
fields,
we
will
refer
several
articles.
introductory
part
provides
a
brief
overview
history
chemistry.
Subsequently,
key
methods
for
preparing
discussed,
followed
by
an
examination
structural
diversity
physical
properties.
main
portion
this
is
dedicated
reactions,
wherein
parent
corresponding
serve
active
species.
It
demonstrated
that
functional
groups
(such
alcohols,
amines,
enolates,
alkanes
among
others)
efficiently
oxidized.
These
oxidations
carried
out
using
catalysts
combination
stoichiometric
terminal
oxidants.
By
reducing
anions,
become
effective
reagents
intriguing
Nitroxides
possess
ability
selectively
react
making
useful
terminating
cascade
reactions
forming
alkoxyamines.
Depending
structure,
alkoxyamines
weak
C–O
bonds,
allowing
thermal
generation
through
reversible
bond
cleavage.
Such
thermally
generated
participate
transformations,
discussed
end
review.
application
strategy
natural
product
synthesis
presented.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(3), P. 1762 - 1768
Published: Jan. 12, 2024
Although
the
C–Hα
functionalization
of
N-heterocycles
is,
in
fact,
an
easy
chemical
transformation,
C–Hβ
on
contrary,
a
quite
difficult
process.
Here,
we
present
two-step
protocol
that
allows
ready
conversion
pyrrolidines,
piperidines,
and
azepane
into
their
corresponding
3-exo-alkenyl
lactams
via
transient
formation
3-alkoxyamino
followed
by
Wittig-like
C(sp3)–O
bond
olefination
with
stabilized
ylides
from
phosphonium
salts
mediated
t-BuOK.
Additionally,
as
proof
synthetic
effectiveness
this
novel
methodology,
first
synthesis
natural
product
callylactam
A
was
achieved
through
TiCl4-catalyzed
double
isomerization
2-piperidone
to
its
endo-isomer.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(3), P. 323 - 329
Published: Jan. 11, 2023
Abstract
With
the
aim
of
providing
an
efficient
platform
for
one‐step
construction
nitrogen‐containing
polycyclic
frameworks,
we
report
a
heterogeneous
platinum‐catalyzed
oxidative
α,β‐C(sp
3
)−H
dual
functionalization
saturated
cyclic
amines.
This
method
involves
tandem
dehydrogenation/hetero
Diels‐Alder
reaction
under
aerobic
mild
conditions,
tetracyclic
octahydro‐dipyrroloquinoline
frameworks
in
good
yields.
The
was
applied
to
synthesis
natural
products
incargranine
B
aglycone
and
seneciobipyrrolidine
one
step.
study
provides
rapid
access
fused
compounds
highly
atom‐economical
fashion.
magnified
image
SynOpen,
Journal Year:
2023,
Volume and Issue:
07(04), P. 718 - 722
Published: Nov. 27, 2023
Abstract
A
methodology
for
the
oxidation
of
alcohols
to
aldehydes
and
ketones
is
presented.
The
approach
employs
catalytic
quantities
a
nitroxide
nitric
acid,
with
no
additives
or
metal
catalysts
being
required.
It
proves
effective
range
aromatic,
heteroaromatic,
aliphatic
alcohol
substrates,
desired
products
formed
in
good
excellent
yield.
In
case
primary
alcohols,
can
be
stopped
at
aldehyde
without
concomitant
formation
corresponding
carboxylic
acid.
Green Synthesis and Catalysis,
Journal Year:
2023,
Volume and Issue:
unknown
Published: Nov. 1, 2023
Herein,
we
reported
an
efficient
and
straightforward
method
to
realize
desaturated
β-C(sp3)-H
sulfonylation
phosphonylation
of
cyclic
amines
driven
by
electrochemistry
using
catalytic
amounts
CP2Fe
as
the
redox
mediator.
This
protocol
which
had
good
functional
group
compatibility,
provided
desired
enaminyl
sulfone
phosphine
oxide
products
with
high
chemo-
regio-selectivity
under
mild
conditions.
Several
mechanistic
studies
have
suggested
that
underwent
multiple
single-electron
oxidation
deprotonation
processes,
followed
a
capture
step
involving
either
sulfonyl
radical
or
phosphonyl
radical,
ultimately
leading
products.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(26), P. 3874 - 3877
Published: Jan. 1, 2023
Oxoammonium
salt-promoted
diverse
functionalization
of
saturated
cyclic
amines
with
different
dinucleophiles
under
mild
conditions
is
presented.
Specifically,
when
thiocyanate
used
as
a
1,3-dinucleophile,
hexahydrothiazolo[4,5-b]pyridin-2(3H)-one
derivatives
are
formed
via
the
formation
β-TEMPO-tethered
iminium
ion
key
intermediate.
By
contrast,
benzene-1,2-diamine
1,4-dinucleophile,
2-alkylquinoxaline
afforded
generation
β-oxo
In
addition,
usefulness
2-alkylquinoxalines
showcased
through
their
facile
conversion
into
N-(2-oxo-2-(quinoxalin-2-yl)ethyl)nitrous
amides
featuring
synthetically
useful
N-NO
moiety
and
carbonyl
group.
