Dynamic Kinetic Activation of Aziridines Enables Radical-Polar Crossover (4 + 3) Cycloaddition with 1,3-Dienes
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 10, 2025
The
cycloaddition
of
aziridines
with
unsaturated
compounds
is
a
valuable
method
for
synthesizing
nitrogen
heterocycles.
However,
this
process
predominantly
substrate-controlled,
posing
significant
challenges
in
regulating
the
regioselectivity
C–N
bond
cleavage.
In
study,
we
report
nickel-catalyzed
dynamic
kinetic
activation
strategy
that
enables
catalyst-controlled
aziridines.
Various
types
aziridines,
including
2-phenyl,
2-carbonyl,
2-alkyl,
and
disubstituted
consistently
cleave
their
more
sterically
hindered
bonds
to
generate
1,3-radical
anion
intermediates.
These
intermediates
participate
highly
regioselective
1,4-Heck/allylic
substitution
cascade
aromatic
branched
1,3-dienes,
resulting
radical-polar
crossover
(4
+
3)
produces
seven-membered
azepine
products.
This
approach
not
only
complements
traditional
dipolar
cycloaddition,
which
typically
act
as
zwitterionic
1,3-dipoles,
but
also
introduces
an
unusual
mode
1,3-dienes.
Experimental
investigations
density
functional
theory
(DFT)
calculations
provide
insight
into
reaction
mechanism.
Язык: Английский
Controllable Radical Reactions of 1,3-Dienes with Light
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 7749 - 7779
Опубликована: Апрель 25, 2025
Язык: Английский
Asymmetric Alkylative Difunctionalization of Carbon‐Carbon Double Bonds by Aliphatic C–H Bond Activation
ChemCatChem,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 27, 2024
Abstract
This
paper
highlights
the
latest
advancements
in
asymmetric
alkylative
difunctionalization
of
carbon–carbon
double
bonds
by
utilizing
aliphatic
C─H
substrates
as
alkyl
radical
precursors.
By
integrating
different
hydrogen
atom
transfer
(HAT)
processes
with
various
transition
metal
catalytic
systems,
alkane
can
be
efficiently
converted
into
corresponding
radicals,
which
then
participate
additions
to
followed
stereoselective
functionalizations
a
third
component.
These
strategies
leverage
inexpensive,
abundant,
and
readily
available
feedstocks
rapidly
construct
complex
chiral
molecules,
demonstrating
high
step
economy.
focuses
on
recent
progress
applications
this
area,
provides
comprehensive
perspective
current
developments,
suggests
future
directions
alkane‐involved
transformations.
Язык: Английский
Indium Mediated Reformatsky-Type Allylation of N-tert-Butanesulfinyl Iminoester with 1,3-Butadiene
Organic Letters,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 20, 2024
This
study
presents
the
indium-mediated
three-component
radical
Reformatsky-type
allylation
of
N-tert-butanesulfinyl
iminoester
with
1,3-butadiene.
novel
approach
offers
a
rapid
synthesis
pathway
to
valuable
homoallylic
noncanonical
amino
acids,
demonstrated
over
30
examples
showing
nice
regio-
and
diastereoselectivity.
Mechanism
studies
revealed
that
allylindium
complexes
served
as
key
intermediates,
formed
through
single-electron
reduction
allylic
radicals
by
Indium
species.
Язык: Английский