Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(13), P. 2058 - 2091
Published: May 17, 2023
Abstract
Decyanation
is
an
important
process
in
the
synthesis
of
aromatic
molecules
studies
pharmaceutical
research,
medical
and
materials
sciences.
In
late‐stage
modifications
privileged
carbo/heterocyclic
scaffolds,
radical‐type
decyanation
techniques
have
been
devised
to
date.
As
a
result,
chemistry
cyano‐involved
conversions,
hotly
debated
subject
over
past
few
decades,
has
advanced
significantly.
The
cyano
group
(CN),
on
other
hand,
rarely
acknowledged
as
good
reaction
site
due
its
thermodynamic
robustness.
most
recent
advancements
catalytic
radical
protocols
that
CN
behaved
leaving
made
are
surveyed
this
article.
Following
introduction
number
different
modes,
reactions
used
activate
C−CN
bonds
primarily
categorized,
text
herein
divided
into
three
groups:
(1)
photo‐catalyzed
transformations,
(2)
electro‐catalyzed
(3)
transition‐metal‐catalyzed
or
metal‐free
transformations.
With
emphasis
systems
synthetic
applications
bond
activation,
review
will
provide
readers
with
overview
reactions.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(13), P. 7587 - 7680
Published: Jan. 1, 2021
Organic
compounds
that
show
Thermally
Activated
Delayed
Fluorescence
(TADF)
have
become
wildly
popular
as
next
generation
emitters
in
organic
light-emitting
diodes
(OLEDs),
but
since
2016,
received
significant
and
increasing
attention
photocatalysts.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2353 - 2428
Published: Oct. 8, 2021
For
more
than
70
years,
nitrogen-centered
radicals
have
been
recognized
as
potent
synthetic
intermediates.
This
review
is
a
survey
designed
for
use
by
chemists
engaged
in
target-oriented
synthesis.
summarizes
the
recent
paradigm
shift
access
to
and
application
of
N-centered
enabled
visible-light
photocatalysis.
broadens
streamlines
approaches
many
small
molecules
because
photocatalysis
conditions
are
mild.
Explicit
attention
paid
innovative
advances
N–X
bonds
radical
precursors,
where
X
=
Cl,
N,
S,
O,
H.
clarity,
key
mechanistic
data
noted,
available.
Synthetic
applications
limitations
summarized
illuminate
tremendous
utility
photocatalytically
generated
radicals.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
143(2), P. 964 - 972
Published: Dec. 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,
Journal Year:
2021,
Volume and Issue:
60(36), P. 19526 - 19549
Published: April 22, 2021
The
use
of
organic
photocatalysts
has
revolutionized
the
field
photoredox
catalysis,
as
it
allows
access
to
reactivities
that
were
traditionally
restricted
transition-metal
photocatalysts.
This
Minireview
reports
recent
developments
in
acridinium
ions
and
cyanoarene
derivatives
synthesis.
activation
inert
chemical
bonds
well
late-stage
functionalization
biorelevant
molecules
are
discussed,
with
a
special
focus
on
their
mechanistic
aspects.
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(19), P. 5659 - 5666
Published: Jan. 1, 2022
General
photoactivation
of
EDA
complexes
between
arylsulfonium
salts
and
1,4-diazabicyclo[2.2.2]octane
was
discovered.
This
practical
mode
enables
the
generation
aryl
radicals
for
C–H
functionalization
arenes.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(36), P. 16219 - 16231
Published: Sept. 2, 2022
The
odyssey
of
photochemistry
is
accompanied
by
the
journey
to
manipulate
"electrons"
and
"protons"
in
time,
space,
energy.
Over
past
decades,
single-electron
(1e-)
photochemical
transformations
have
brought
marvelous
achievements.
However,
as
each
photon
absorption
typically
generates
only
one
exciton
pair,
it
exponentially
challenging
accomplish
multielectron
proton
transformations.
multistep
differences
thermodynamics
kinetics
urgently
require
us
optimize
light
harvesting,
expedite
consecutive
electron
transfer,
interaction
catalysts
with
substrates,
coordinate
transfer
furnish
selective
bond
formations.
Tandem
catalysis
enables
orchestrating
different
events
catalytic
from
subpicoseconds
seconds,
which
facilitates
redox
chemistries
brings
consecutive,
value-added
reactivities.
Joint
efforts
molecular
material
design,
mechanistic
understanding,
theoretical
modeling
will
bring
synthetic
opportunities
for
fuels,
fertilizers,
chemicals
enhanced
versatility,
efficiency,
selectivity,
scalability,
thus
taking
better
advantage
photons
(i.e.,
sunlight)
our
sustainable
society.
Science,
Journal Year:
2024,
Volume and Issue:
383(6684), P. 750 - 756
Published: Feb. 15, 2024
Water
can
accelerate
a
variety
of
organic
reactions
far
beyond
the
rates
observed
in
classical
solvents.
However,
using
pure
water
as
solvent
introduces
solubility
constraints
that
have
limited
applicability
efficient
photochemistry
particular.
We
report
here
formation
aggregates
between
pairs
arenes,
heteroarenes,
enamines,
or
esters
with
different
electron
affinities
an
aqueous
medium,
leading
to
oil-water
phase
boundary
through
substrate
melting
point
depression.
The
active
hydrogen
atoms
reactants
engage
bonds
water,
thereby
accelerating
photochemical
reactions.
This
methodology
realizes
appealingly
simple
conditions
for
coupling
complex
solid
molecules,
including
drug
molecules
are
poorly
soluble
water.
