Research Square (Research Square),
Год журнала:
2023,
Номер
unknown
Опубликована: Окт. 30, 2023
Abstract
Numerous
applications
of
alkenes
exist
due
to
their
abundance
and
versatility
in
chemical
transformations.
In
this
study,
we
present
a
unique
novel
transformation
alkenes,
the
aza-version
canonical
ozonolysis
reaction,
which
termed
as
triazenolysis.
This
process
offers
non-trivial
previously
unfeasible
synthetic
disconnection,
allowing
cleavage
C=C
double
bond
into
two
new
C-N
bonds
reductive
manner.
We
carefully
examined
applicability
finding
that
diverse
cyclic
are
suitable
for
developed
process.
Furthermore,
an
example
acyclic
alkene,
illustrating
potential
expanding
triazenolysis
other
counterparts.
Through
DFT
calculations,
explored
mechanism
key
step
demonstrated
significance
Lewis
acid
catalysis
achieving
desired
transformation.
Abstract
N-Heterocyclic
nitreniums
(NHNs)
are
isoelectronic
and
isostructural
analogues
of
N-heterocyclic
carbenes
(NHCs).
Unlike
NHCs,
NHNs
much
less
developed.
While
a
comprehensive
understanding
NHN
reactivity
remains
elusive,
recent
advancements
have
demonstrated
their
utility
as
Lewis
acid
catalysts,
photoreductants,
photooxidants,
leading
to
several
reaction
patterns.
In
this
short
review,
we
focus
on
the
applications
in
photoredox
reactions.
We
also
discuss
mechanisms
behind
these
transformations
outline
future
research
directions.
1
Introduction
2
Application
Nitreniums
Photoreductants
3
Facilitate
Photohomolysis
4
Photooxidants
5
Conclusion
Organic & Biomolecular Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
An
efficient
photoactive
charge
transfer
complex
protocol
for
the
synthesis
of
phenanthridine
derivatives
by
reaction
2-isocyanobiaryls
with
α-chloro
esters
is
established.
The Journal of Physical Chemistry A,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 17, 2025
Cyclic
nitrenium
ions
(CNIs)
are
generally
stable
and
have
found
applications
in
chemistry,
including
biochemistry.
five-membered
1,2,3-triazolium
(CFTIs)
a
special
class
of
CNIs;
such
moieties
few
medicinally
important
species.
Though
they
isoelectronic
to
N-heterocyclic
carbenes
(NHCs),
exhibit
electrophilic
properties
(unlike
nucleophilic
NHCs).
A
quantum
chemical
studies
were
reported,
but
extensive
study
on
CFTIs
is
required
understand
their
electronic
features
design
species
with
tailored
properties.
In
this
work,
thorough
analysis
has
been
carried
out
the
standard
CFTI
(1,3-dimethyl-1,2,3-triazolium
ion).
Hydride
ion
affinity
fluoride
parameters
estimated
evaluate
Lewis
acidic
character
CFTIs.
Also,
electrophilicity
these
terms
global
index
(ω)
values.
The
complexation
energies
PMe3
(ΔHPMe3)
1,3-dimethylimidazol-2-ylidene
(ΔHNHC)
also
estimated.
modulation
as
function
substitution
ring
fusion
evaluated.
correlation
between
ΔHPMe3
ΔHNHC
very
high
(R
=
0.99);
helps
identifying
that
may
character.
Considering
the
appealing
synthetic
properties
of
oxygenous
feedstocks
and
organoboron
compounds,
direct
deoxygenative
borylation
is
a
very
desirable
chemical
transformation.
Directly
converting
acyl
chlorides
into
alkylboronates
through
an
unknown
but
valuable
reaction.
Herein,
relatively
straightforward
one‐step
methodology
reported
where
N‐heterocyclic
nitrenium
(NHN)
ion
acts
as
photocatalyst
under
visible
light
to
produce
benzylboronates
directly
from
aroyl
in
absence
metals
or
additives.
A
large
variety
are
well
tolerated
reaction
conditions.
Mechanistic
investigations
density
functional
theory
calculations
support
that
NHN
species
involved
radical
formation
DMAc‐H
2
O/B
cat
contributes
alkylboronates.
Green Synthesis and Catalysis,
Год журнала:
2024,
Номер
unknown
Опубликована: Март 1, 2024
The
photoredox
radical-polar
crossover
paradigm
is
a
valuable
tool
for
1,2-difunctionalization
of
alkenes.
However,
the
use
unactivated
alkyl
halides
as
radical
precursors
remains
far
less
developed.
Here,
we
report
photoreductive
N-heterocyclic
nitrenium-catalyzed
1,2-dicarbofunctionalization
alkenes
by
using
and
aryl
iodides.
These
reactions
can
be
carried
out
under
simple,
transition-metal-free
conditions
with
easily
obtainable
materials
such
alkyl/aryl
halides,
alkenes,
aldehydes.
exhibit
broad
range
substrate
compatibility
good
tolerance
towards
functional
groups.
This
approach
offers
new
to
unlock
carbon
skeletons.
Asian Journal of Organic Chemistry,
Год журнала:
2023,
Номер
12(6)
Опубликована: Апрель 22, 2023
Abstract
Herein,
we
developed
a
fluoride‐mediated
nucleophilic
aromatic
amination
of
chloro‐1
H
‐1,2,3‐triazolium
salts.
Various
functional
groups
were
tolerated
in
this
reaction,
which
enabled
the
synthesis
functionalized
amino‐1
In
addition,
investigated
catalytic
properties
triazolium‐based
N‐heterocyclic
imines
(NHIs)
for
cyanosilylation
ketones.
The
substituent
was
found
to
play
crucial
role
inducing
high
activity.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
11(3), С. 673 - 683
Опубликована: Ноя. 28, 2023
We
report
an
efficient
and
versatile
catalytic
N-heterocyclic
nitrenium
charge
transfer
complex
strategy
for
the
single-electron
reduction
of
chloroform,
resulting
in
generation
dichloromethyl
radical
use
various
transformations.
Chemical Science,
Год журнала:
2023,
Номер
14(43), С. 12034 - 12040
Опубликована: Янв. 1, 2023
Bench-stable
N-heterocyclic
nitrenium
ions
were
used
for
the
efficient
electrophilic
amination
of
organometallic
nucleophiles.
The
previously
unexplored
N
-alkyl/aryl
triazane
intermediates
reduced
to
produce
a
diverse
scope
primary
amines.
Journal of Computational Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 30, 2024
Abstract
Cyclic
nitrenium
ions
containing
five‐membered
and
six‐membered
rings
are
available,
however,
the
seven‐membered
cyclic
(azepinium
ions)
rare.
The
chemistry
of
these
species
is
related
to
their
stability
originating
from
aromaticity
due
6π
electrons.
Very
few
theoretical
experimental
studies
have
been
conducted
on
azepinium
ions.
Related
clozapine
olanzapine
cations
(diazepinium
were
observed
during
drug
metabolism
studies.
In
this
work,
quantum
chemical
analysis
has
carried
out
estimate
stability,
aromaticity,
electrophilicity
several
derivatives
A
designed
carry
Δ
E
S‐T
values
in
range
50
kcal/mol
favoring
singlet
state;
π
donating
groups
at
2nd
position
increase
singlet‐triplet
energy
differences.
Most
substituents
reduce
NICS(1)
compared
parent
system.
Ring
fusion
with
heterocyclic
generally
increases
ion
ring
systems.
parameters
estimated
terms
HIA,
FIA,
ω
indicate
that
it
possible
fine‐tune
properties
appropriate
modulation.
