Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(16)
Published: Jan. 29, 2024
Abstract
We
highlight
key
contributions
in
the
field
of
direct
radical
C
Ar
−
H
(hetero)aromatic
functionalization
involving
fluorinated
radicals.
A
compilation
Functional
Group
Transfer
Reagents
and
their
diverse
activation
mechanisms
leading
to
release
radicals
are
discussed.
The
substrate
scope
for
each
is
analyzed
classified
into
three
categories
according
electronic
properties
substrates.
Density
functional
theory
computational
analysis
provides
insights
chemical
reactivity
several
through
electrophilicity
nucleophilicity
parameters.
Theoretical
reduction
potentials
also
highlights
remarkable
correlation
between
oxidizing
ability.
It
established
that
highly
(e.g.
⋅OCF
3
)
capable
engaging
single‐electron
transfer
(SET)
processes
rather
than
addition,
which
good
agreement
with
experimental
literature
data.
scale,
based
on
barrier
addition
these
benzene
elaborated
using
high
accuracy
DLPNO‐(U)CCSD(T)
method.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(14), P. 7941 - 8002
Published: Jan. 1, 2021
Electrochemistry
has
recently
gained
increased
attention
as
a
versatile
strategy
for
achieving
challenging
transformations
at
the
forefront
of
synthetic
organic
chemistry.
Electrochemistry's
unique
ability
to
generate
highly
reactive
radical
and
ion
intermediates
in
controlled
fashion
under
mild
conditions
inspired
development
number
new
electrochemical
methodologies
preparation
valuable
chemical
motifs.
Particularly,
recent
developments
electrosynthesis
have
featured
an
use
redox-active
electrocatalysts
further
enhance
control
over
selective
formation
downstream
reactivity
these
intermediates.
Furthermore,
electrocatalytic
mediators
enable
proceed
manner
that
is
mechanistically
distinct
from
purely
methods,
allowing
subversion
kinetic
thermodynamic
obstacles
encountered
conventional
synthesis.
This
review
highlights
key
innovations
within
past
decade
area
electrocatalysis,
with
emphasis
on
mechanisms
catalyst
design
principles
underpinning
advancements.
A
host
oxidative
reductive
are
discussed
grouped
according
classification
transformation
nature
electrocatalyst.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2752 - 2906
Published: Aug. 10, 2021
Photoinduced
chemical
transformations
have
received
in
recent
years
a
tremendous
amount
of
attention,
providing
plethora
opportunities
to
synthetic
organic
chemists.
However,
performing
photochemical
transformation
can
be
quite
challenge
because
various
issues
related
the
delivery
photons.
These
challenges
barred
widespread
adoption
steps
industry.
past
decade,
several
technological
innovations
led
more
reproducible,
selective,
and
scalable
photoinduced
reactions.
Herein,
we
provide
comprehensive
overview
these
exciting
advances,
including
flow
chemistry,
high-throughput
experimentation,
reactor
design
scale-up,
combination
photo-
electro-chemistry.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2487 - 2649
Published: Nov. 9, 2021
Redox
processes
are
at
the
heart
of
synthetic
methods
that
rely
on
either
electrochemistry
or
photoredox
catalysis,
but
how
do
and
catalysis
compare?
Both
approaches
provide
access
to
high
energy
intermediates
(e.g.,
radicals)
enable
bond
formations
not
constrained
by
rules
ionic
2
electron
(e)
mechanisms.
Instead,
they
1e
mechanisms
capable
bypassing
electronic
steric
limitations
protecting
group
requirements,
thus
enabling
chemists
disconnect
molecules
in
new
different
ways.
However,
while
providing
similar
intermediates,
differ
several
physical
chemistry
principles.
Understanding
those
differences
can
be
key
designing
transformations
forging
disconnections.
This
review
aims
highlight
these
similarities
between
comparing
their
underlying
principles
describing
impact
electrochemical
photochemical
methods.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
59(29), P. 11732 - 11747
Published: Dec. 5, 2019
Photoredox
catalysis
(PRC)
and
synthetic
organic
electrochemistry
(SOE)
are
often
considered
competing
technologies
in
synthesis.
Their
fusion
has
been
largely
overlooked.
We
review
state-of-the-art
photoelectrochemistry,
grouping
examples
into
three
categories:
1)
electrochemically
mediated
photoredox
(e-PRC),
2)
decoupled
photoelectrochemistry
(dPEC),
3)
interfacial
(iPEC).
Such
synergies
prove
beneficial
not
only
for
"greenness"
chemical
selectivity,
but
also
the
accumulation
of
energy
accessing
super-oxidizing
or
-reducing
single
electron
transfer
(SET)
agents.
Opportunities
challenges
this
emerging
exciting
field
discussed.
Chemical Society Reviews,
Journal Year:
2020,
Volume and Issue:
50(2), P. 766 - 897
Published: Dec. 22, 2020
Recent
developments
and
future
prospects
of
visible-light
photocatalysis
in
the
late-stage
functionalization
pharmaceuticals
natural
bioactive
compounds.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(8), P. 4237 - 4352
Published: Jan. 24, 2023
The
emergence
of
modern
photocatalysis,
characterized
by
mildness
and
selectivity,
has
significantly
spurred
innovative
late-stage
C–H
functionalization
approaches
that
make
use
low
energy
photons
as
a
controllable
source.
Compared
to
traditional
strategies,
photocatalysis
paves
the
way
toward
complementary
and/or
previously
unattainable
regio-
chemoselectivities.
Merging
compelling
benefits
with
workflow
offers
potentially
unmatched
arsenal
tackle
drug
development
campaigns
beyond.
This
Review
highlights
photocatalytic
strategies
small-molecule
drugs,
agrochemicals,
natural
products,
classified
according
targeted
bond
newly
formed
one.
Emphasis
is
devoted
identifying,
describing,
comparing
main
mechanistic
scenarios.
draws
critical
comparison
between
established
ionic
chemistry
photocatalyzed
radical-based
manifolds.
aims
establish
current
state-of-the-art
illustrate
key
unsolved
challenges
be
addressed
in
future.
authors
aim
introduce
general
readership
functionalization,
specialist
practitioners
evaluation
methodologies,
potential
for
improvement,
future
uncharted
directions.
