Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 5, 2024
Abstract
Given
the
unique
charm
of
dipole
chemistry,
intercepting
N−O=C
dipoles
precisely
generated
by
designed
processes
to
develop
novel
reactivity
has
become
a
seminal
challenge.
The
polar
fragmentation
1,3,2‐dioxazolidine
species
through
radical
addition
excited
nitro(hetero)arenes
alkenes
represents
significantly
underappreciated
mechanism
for
generating
dipoles.
Herein,
we
present
photoinduced
Bartoli
indole
synthesis
oxidative
cleavage
with
nitro(hetero)arenes.
Various
indoles
and
azaindoles
are
constructed
multi‐step
spontaneous
rearrangement
carbonyl
imine
intermediates
species.
Mechanism
studies
DFT
calculations
support
that
reaction
involves
cycloaddition,
ozonolysis‐type
cycloreversion,
intramolecular
H‐shift
imines,
3,3‐sigmatropic
shift
O‐Alkenyl
hydroxylamines,
etc.
implementation
continuous‐
flow
photochemistry,
in
particular,
enhances
efficiency,
thereby
overcoming
obstacles
commercialization
process.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 14, 2024
We
report
a
visible
light-mediated
[1
+
2
2]
cycloaddition
reaction
between
nitroarenes
and
alkenes,
conducted
under
mild
conditions,
to
synthesize
isoxazolidines.
Science Advances,
Journal Year:
2024,
Volume and Issue:
10(18)
Published: May 1, 2024
Polyfunctionalized
arenes
are
privileged
structural
motifs
in
both
academic
and
industrial
chemistry.
Conventional
methods
for
accessing
this
class
of
chemicals
usually
involve
stepwise
modification
phenyl
rings,
often
necessitating
expensive
noble
metal
catalysts
suffering
from
low
reactivity
selectivity
when
introducing
multiple
functionalities.
We
herein
report
dehydrogenative
synthesis
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 23, 2024
Abstract
Acridine
frameworks
stand
as
pivotal
architectural
elements
in
pharmaceuticals
and
photocatalytic
applications,
owing
to
their
chemical
adaptability,
biological
activity,
unique
excited‐state
dynamics.
Conventional
synthetic
routes
often
entail
specialized
starting
materials,
anaerobic
or
moisture‐free
conditions,
elaborate
multi‐stage
manipulations
for
incorporating
diverse
functionalities.
Herein,
we
present
a
convergent
approach
integrating
photo‐excitation
of
readily
available
ortho
‐alkyl
nitroarenes
with
copper‐promoted
cascade
annulation.
This
innovative
system
enables
an
aerobic,
one‐pot
reaction
o‐
alkyl
arylboronic
acids,
thereby
streamlining
the
modular
construction
wide
array
acridine
derivatives
various
functional
groups.
encompasses
symmetrical,
unsymmetrical
polysubstituted
varieties,
some
which
are
otherwise
exceptionally
difficult
synthesize.
Furthermore,
it
significantly
improves
production
structurally
varied
acridinium
salts,
featuring
enhanced
photophysical
properties,
high
excited
state
potentials
(
E
*
red
=2.08–3.15
V),
exhibiting
superior
performance
intricate
photoredox
transformations.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(42)
Published: July 23, 2024
Abstract
Acridine
frameworks
stand
as
pivotal
architectural
elements
in
pharmaceuticals
and
photocatalytic
applications,
owing
to
their
chemical
adaptability,
biological
activity,
unique
excited‐state
dynamics.
Conventional
synthetic
routes
often
entail
specialized
starting
materials,
anaerobic
or
moisture‐free
conditions,
elaborate
multi‐stage
manipulations
for
incorporating
diverse
functionalities.
Herein,
we
present
a
convergent
approach
integrating
photo‐excitation
of
readily
available
ortho
‐alkyl
nitroarenes
with
copper‐promoted
cascade
annulation.
This
innovative
system
enables
an
aerobic,
one‐pot
reaction
o‐
alkyl
arylboronic
acids,
thereby
streamlining
the
modular
construction
wide
array
acridine
derivatives
various
functional
groups.
encompasses
symmetrical,
unsymmetrical
polysubstituted
varieties,
some
which
are
otherwise
exceptionally
difficult
synthesize.
Furthermore,
it
significantly
improves
production
structurally
varied
acridinium
salts,
featuring
enhanced
photophysical
properties,
high
excited
state
potentials
(
E
*
red
=2.08–3.15
V),
exhibiting
superior
performance
intricate
photoredox
transformations.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 5, 2024
Abstract
Given
the
unique
charm
of
dipole
chemistry,
intercepting
N−O=C
dipoles
precisely
generated
by
designed
processes
to
develop
novel
reactivity
has
become
a
seminal
challenge.
The
polar
fragmentation
1,3,2‐dioxazolidine
species
through
radical
addition
excited
nitro(hetero)arenes
alkenes
represents
significantly
underappreciated
mechanism
for
generating
dipoles.
Herein,
we
present
photoinduced
Bartoli
indole
synthesis
oxidative
cleavage
with
nitro(hetero)arenes.
Various
indoles
and
azaindoles
are
constructed
multi‐step
spontaneous
rearrangement
carbonyl
imine
intermediates
species.
Mechanism
studies
DFT
calculations
support
that
reaction
involves
cycloaddition,
ozonolysis‐type
cycloreversion,
intramolecular
H‐shift
imines,
3,3‐sigmatropic
shift
O‐Alkenyl
hydroxylamines,
etc.
implementation
continuous‐
flow
photochemistry,
in
particular,
enhances
efficiency,
thereby
overcoming
obstacles
commercialization
process.
