Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
57(48), P. 15664 - 15669
Published: Oct. 8, 2018
Abstract
The
selective
functionalization
of
chemically
inert
C−H
bonds
remains
to
be
fully
realized
in
achieving
organic
transformations
that
are
redox‐neutral,
waste‐limiting,
and
atom‐economical.
catalytic
generation
chlorine
atoms
from
chloride
ions
is
one
the
most
challenging
redox
processes,
where
requirement
harsh
oxidizing
reaction
conditions
renders
it
seldom
utilized
synthetic
applications.
We
report
mild,
controlled,
as
a
new
opportunity
for
access
wide
variety
hydrogen
atom
transfer
(HAT)
reactions
owing
high
stability
HCl.
discovery
photoredox
mediated
with
Ir‐based
polypyridyl
complex,
[Ir(dF(CF
3
)ppy)
2
(dtbbpy)]Cl,
under
blue
LED
irradiation
reported.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(12), P. 5461 - 5476
Published: March 5, 2020
The
association
of
an
electron-rich
substrate
with
electron-accepting
molecule
can
generate
a
new
molecular
aggregate
in
the
ground
state,
called
electron
donor-acceptor
(EDA)
complex.
Even
when
two
precursors
do
not
absorb
visible
light,
resulting
EDA
complex
often
does.
In
1952,
Mulliken
proposed
quantum-mechanical
theory
to
rationalize
formation
such
colored
complexes.
However,
and
besides
few
pioneering
studies
20th
century,
it
is
only
past
years
that
photochemistry
has
been
recognized
as
powerful
strategy
for
expanding
potential
visible-light-driven
radical
synthetic
chemistry.
Here,
we
explain
why
this
photochemical
approach
was
overlooked
so
long.
We
critically
discuss
historical
context,
scientific
reasons,
serendipitous
observations,
landmark
discoveries
were
essential
progress
field.
also
outline
future
directions
identify
key
advances
are
needed
fully
exploit
photochemistry.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 1875 - 1924
Published: Aug. 6, 2021
Direct
photocatalyzed
hydrogen
atom
transfer
(d-HAT)
can
be
considered
a
method
of
choice
for
the
elaboration
aliphatic
C–H
bonds.
In
this
manifold,
photocatalyst
(PCHAT)
exploits
energy
photon
to
trigger
homolytic
cleavage
such
bonds
in
organic
compounds.
Selective
bond
may
achieved
by
judicious
abstractor
(key
parameters
are
electronic
character
and
molecular
structure),
as
well
reaction
additives.
Different
classes
PCsHAT
available,
including
aromatic
ketones,
xanthene
dyes
(Eosin
Y),
polyoxometalates,
uranyl
salts,
metal-oxo
porphyrin
tris(amino)cyclopropenium
radical
dication.
The
processes
(mainly
C–C
formation)
most
cases
carried
out
under
mild
conditions
with
help
visible
light.
aim
review
is
offer
comprehensive
survey
synthetic
applications
d-HAT.
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
58(12), P. 3730 - 3747
Published: Oct. 19, 2018
Abstract
The
fast‐moving
fields
of
photoredox
and
photocatalysis
have
recently
provided
fresh
opportunities
to
expand
the
potential
synthetic
organic
chemistry.
Advances
in
light‐mediated
processes
mainly
been
guided
so
far
by
empirical
findings
quest
for
reaction
invention.
general
perception,
however,
is
that
entering
a
more
mature
phase
where
combination
experimental
mechanistic
studies
will
play
dominant
role
sustaining
further
innovation.
This
Review
outlines
key
consider
when
developing
photochemical
process,
best
techniques
available
acquiring
relevant
information.
discussion
use
selected
case
highlight
how
investigations
can
be
instrumental
guiding
invention
development
synthetically
useful
photocatalytic
transformations.
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.
Science,
Journal Year:
2018,
Volume and Issue:
360(6387), P. 419 - 422
Published: April 5, 2018
Basic
heteroarenes
are
a
ubiquitous
feature
of
pharmaceuticals
and
bioactive
molecules,
Minisci-type
additions
radical
nucleophiles
leading
method
for
their
elaboration.
Despite
many
protocols
that
result
in
the
formation
stereocenters,
exerting
control
over
absolute
stereochemistry
at
these
centers
remains
an
unmet
challenge.
We
report
process
addition
prochiral
radicals,
generated
from
amino
acid
derivatives,
to
pyridines
quinolines.
Our
offers
excellent
both
enantioselectivity
regioselectivity.
An
enantiopure
chiral
Brønsted
catalyst
serves
activate
substrate
induce
asymmetry,
while
iridium
photocatalyst
mediates
required
electron
transfer
processes.
anticipate
this
will
expedite
access
enantioenriched
small-molecule
building
blocks
bearing
versatile
basic
heterocycles.
Chemical Reviews,
Journal Year:
2020,
Volume and Issue:
120(17), P. 9790 - 9833
Published: Aug. 6, 2020
Alkyl
radicals
are
key
intermediates
in
organic
synthesis.
Their
classic
generation
from
alkyl
halides
has
a
severe
drawback
due
to
the
employment
of
toxic
tin
hydrides
point
that
"flight
tyranny
tin"
radical
processes
was
considered
for
long
time
an
unavoidable
issue.
This
review
summarizes
main
alternative
approaches
unstabilized
radicals,
using
photons
as
traceless
promoters.
The
recent
development
photochemical
and
photocatalyzed
enabled
discovery
plethora
new
precursors,
opening
world
chemistry
broader
community,
thus
allowing
era
photon
democracy.
Nature Communications,
Journal Year:
2020,
Volume and Issue:
11(1)
Published: Feb. 6, 2020
Can
organic
chemistry
mimic
nature
in
efficiency
and
sustainability?
Not
yet,
but
recent
developments
photoredox
catalysis
animated
the
synthetic
field,
providing
greener
opportunities
for
industry
academia.
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.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(3), P. 1522 - 1586
Published: Jan. 1, 2021
This
review
provides
a
comprehensive
overview
of
the
recent
applications
organocatalytic
strategies
in
pharmaceutical
synthesis,
with
focus
on
preparation
antiviral,
anticancer,
neuroprotective,
cardiovascular,
antibacterial
and
antiparasitic
agents.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 1654 - 1716
Published: Oct. 4, 2021
Asymmetric
catalysis
is
a
major
theme
of
research
in
contemporary
synthetic
organic
chemistry.
The
discovery
general
strategies
for
highly
enantioselective
photochemical
reactions,
however,
has
been
relatively
recent
development,
and
the
variety
photoreactions
that
can
be
conducted
stereocontrolled
manner
consequently
somewhat
limited.
photocatalysis
complicated
by
short
lifetimes
high
reactivities
characteristic
photogenerated
reactive
intermediates;
design
catalyst
architectures
provide
effective
enantiodifferentiating
environments
these
intermediates
while
minimizing
participation
uncontrolled
racemic
background
processes
proven
to
key
challenge
progress
this
field.
This
review
provides
summary
chiral
structures
have
studied
solution-phase
asymmetric
photochemistry,
including
sensitizers,
inorganic
chromophores,
soluble
macromolecules.
While
some
photocatalysts
are
derived
from
privileged
both
ground-state
transformations,
others
structural
designs
unique
offer
insight
into
logic
required
photocatalysis.