Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
61(12)
Опубликована: Сен. 3, 2021
Synthetic
photoelectrochemistry
(PEC)
is
receiving
increasing
attention
as
a
new
frontier
for
the
generation
and
handling
of
reactive
intermediates.
PEC
permits
selective
single-electron
transfer
(SET)
reactions
in
much
greener
way
broadens
redox
window
possible
transformations.
Herein,
most
recent
contributions
are
reviewed,
demonstrating
exciting
opportunities,
namely,
combination
with
other
reactivity
paradigms
(hydrogen-atom
transfer,
radical
polar
crossover,
energy
sensitization),
scalability
up
to
multigram
scale,
novel
selectivities
SET
super-oxidations/reductions
importance
precomplexation
temporally
enable
excited
ion
catalysis.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(33), С. 13266 - 13273
Опубликована: Авг. 16, 2021
Since
the
seminal
work
of
Zhang
in
2016,
donor–acceptor
cyanoarene-based
fluorophores,
such
as
1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene
(4CzIPN),
have
been
widely
applied
photoredox
catalysis
and
used
excellent
metal-free
alternatives
to
noble
metal
Ir-
Ru-based
photocatalysts.
However,
all
reported
reactions
involving
this
chromophore
family
are
based
on
harnessing
energy
from
a
single
visible
light
photon,
with
limited
range
redox
potentials
−1.92
+1.79
V
vs
SCE.
Here,
we
document
unprecedented
discovery
that
fluorophores
can
undergo
consecutive
photoinduced
electron
transfer
(ConPET)
achieve
very
high
reduction
potentials.
One
newly
synthesized
catalysts,
2,4,5-tri(9H-carbazol-9-yl)-6-(ethyl(phenyl)amino)isophthalonitrile
(3CzEPAIPN),
possesses
long-lived
(12.95
ns)
excited
radical
anion
form,
3CzEPAIPN•–*,
which
be
activate
reductively
recalcitrant
aryl
chlorides
(Ered
≈
−1.9
−2.9
SCE)
under
mild
conditions.
The
resultant
radicals
engaged
synthetically
valuable
aromatic
C–B,
C–P,
C–C
bond
formation
furnish
arylboronates,
arylphosphonium
salts,
arylphosphonates,
spirocyclic
cyclohexadienes.
Journal of the American Chemical Society,
Год журнала:
2020,
Номер
143(2), С. 964 - 972
Опубликована: Дек. 29, 2020
2,4,5,6-Tetrakis(3,6-di-tert-butyl-9H-carbazol-9-yl)isophthalonitrile
(4CzIPN-tBu)
was
developed
as
a
photocatalyst
for
the
phosphorus-radical-initiated
cascade
cyclization
reaction
of
isocyanides.
By
using
4CzIPN-tBu
catalyst,
we
visible-light-induced
proton-coupled
electron
transfer
strategy
generation
phosphorus-centered
radicals,
via
which
wide
range
phosphorylated
phenanthridines,
quinolines,
and
benzothiazoles
were
successfully
constructed.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
61(12)
Опубликована: Сен. 3, 2021
Synthetic
photoelectrochemistry
(PEC)
is
receiving
increasing
attention
as
a
new
frontier
for
the
generation
and
handling
of
reactive
intermediates.
PEC
permits
selective
single-electron
transfer
(SET)
reactions
in
much
greener
way
broadens
redox
window
possible
transformations.
Herein,
most
recent
contributions
are
reviewed,
demonstrating
exciting
opportunities,
namely,
combination
with
other
reactivity
paradigms
(hydrogen-atom
transfer,
radical
polar
crossover,
energy
sensitization),
scalability
up
to
multigram
scale,
novel
selectivities
SET
super-oxidations/reductions
importance
precomplexation
temporally
enable
excited
ion
catalysis.
