Excited Organic Radicals in Photoredox Catalysis
JACS Au,
Год журнала:
2025,
Номер
5(2), С. 426 - 447
Опубликована: Янв. 29, 2025
Many
important
synthetic-oriented
works
have
proposed
excited
organic
radicals
as
photoactive
species,
yet
mechanistic
studies
raised
doubts
about
whether
they
can
truly
function
photocatalysts.
This
skepticism
originates
from
the
formation
of
(photo)redox-active
degradation
products
and
picosecond
decay
electronically
radicals,
which
is
considered
too
short
for
diffusion-based
photoinduced
electron
transfer
reactions.
From
this
perspective,
we
analyze
synthetic
transformations
where
been
photocatalysts,
comparing
their
theoretical
maximum
state
potentials
with
required
observed
photocatalytic
reactivity.
We
summarize
structurally
similar
photocatalysts
indicating
different
reaction
pathways
some
catalytic
systems,
addressing
cases
radical
exceed
Additionally,
perform
a
kinetic
analysis
to
explain
in
on
subpicosecond
time
scales.
further
rationalize
potential
anti-Kasha
reactivity
higher
states
femtosecond
lifetimes,
highlighting
how
future
photocatalysis
advancements
could
unlock
new
photochemical
pathways.
Язык: Английский
Bench-Stable Meisenheimer Complexes: Synthesis, Characterization, and Divergent Reactivity for Dearomatization
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(45), С. 30764 - 30770
Опубликована: Окт. 30, 2024
The
chemistry
of
the
Meisenheimer
complexes
is
fundamental
interest
in
organic
chemistry.
While
nitro
group
has
been
extensively
employed
to
facilitate
formation
and
stabilization
complexes,
analogous
application
more
user-friendly
ester
groups
remained
an
unexplored
frontier.
Herein,
we
report
ester-stabilized
which
have
remarkable
air-,
moisture-,
thermo-stability.
Moreover,
isolable
well-defined
intermediates
exhibit
divergent
reactivity
for
dearomatization
reactions,
including
modular
1,4-additions,
dearomative
(2
+
3)
cycloadditions,
even
higher-order
(4
Язык: Английский