Organic Letters,
Год журнала:
2021,
Номер
23(14), С. 5349 - 5353
Опубликована: Июнь 28, 2021
A
mild
transition-metal-
and
photosensitizer-free
photoredox
system
based
on
the
combination
of
NaI
PPh3
was
found
to
enable
highly
selective
reduction
nitroarenes.
This
protocol
tolerates
a
broad
range
reducible
functional
groups
such
as
halogen
(Cl,
Br,
even
I),
aldehyde,
ketone,
carboxyl,
cyano.
Moreover,
catalysis
with
stoichiometric
provides
also
an
alternative
entry
Cadogan-type
reductive
amination
when
o-nitrobiarenes
were
used.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(13), С. 7587 - 7680
Опубликована: Янв. 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,
Год журнала:
2023,
Номер
123(8), С. 4237 - 4352
Опубликована: Янв. 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.
Nature Communications,
Год журнала:
2021,
Номер
12(1)
Опубликована: Июнь 29, 2021
Abstract
Hydrogen
atom
abstraction
(HAT)
from
C(
sp
3
)–H
bonds
of
naturally
abundant
alkanes
for
alkyl
radical
generation
represents
a
promising
yet
underexplored
strategy
in
the
alkylation
reaction
designs
since
involving
stoichiometric
oxidants,
excessive
alkane
loading,
and
limited
scope
are
common
drawbacks.
Here
we
report
photo-induced
chemical
oxidant-free
cross-dehydrogenative
coupling
(CDC)
between
heteroarenes
using
catalytic
chloride
cobalt
catalyst.
Couplings
strong
bond-containing
substrates
complex
heteroarenes,
have
been
achieved
with
satisfactory
yields.
This
dual
platform
features
situ
engendered
chlorine
exploits
cobaloxime
catalyst
to
enable
hydrogen
evolution
turnover.
The
practical
value
this
protocol
was
demonstrated
by
gram-scale
synthesis
alkylated
heteroarene
merely
equiv.
loading.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(9), С. 5349 - 5365
Опубликована: Янв. 1, 2021
Ketyl
radicals
are
valuable
reactive
intermediates
for
synthesis
and
used
extensively
to
construct
complex,
functionalized
products
from
carbonyl
substrates.
Single
electron
transfer
(SET)
reduction
of
the
C[double
bond,
length
as
m-dash]O
bond
aldehydes
ketones
is
classical
approach
formation
ketyl
metal
reductants
archetypal
reagents
employed.
The
past
decade
has,
however,
witnessed
significant
advances
in
generation
harnessing
radicals.
This
tutorial
review
highlights
recent,
exciting
developments
chemistry
by
comparing
varied
contemporary
-
example,
using
photoredox
catalysts
more
approaches
use
will
focus
on
different
strategies
radical
generation,
their
creative
new
synthetic
protocols,
control
enantioselectivity,
detailed
mechanisms
where
appropriate.
European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
2022(34)
Опубликована: Май 13, 2022
Abstract
The
opportunity
to
activate
C(sp
3
)−H
bonds
via
homolytic
cleavage
by
means
of
halogen
radicals
has
long
been
disregarded
in
synthetic
endeavors
due
the
unpredictable
selectivity.
Nowadays,
photocatalysis
established
itself
as
a
method
choice
for
generation
such
reactive
intermediates
under
mild
conditions.
This
Minireview
collects
recent
examples
showcasing
how
photocatalytic
manifolds
have
used
tame
aggressive
Hydrogen
Atom
Transfer
(HAT)
purposes.
In
last
section
this
work,
we
address
site‐selectivity
issues
posed
methodology
and
show
it
can
be
guided
through
judicious
reaction
Green Chemistry,
Год журнала:
2023,
Номер
25(5), С. 1975 - 1981
Опубликована: Янв. 1, 2023
This
study
describes
a
green
and
sustainable
photoinduced
strategy
for
decarboxylative
C–H
(amino)alkylation
of
heteroarenes
with
carboxylic
acids
under
metal-
photosensitizer-free
conditions.
Green Chemistry,
Год журнала:
2024,
Номер
26(12), С. 7331 - 7336
Опубликована: Янв. 1, 2024
A
novel
photocatalytic
acylation
strategy
was
developed
harnessing
tetrabutylammonium
decatungstate
(TBADT)
as
a
hydrogen
atom
transfer
(HAT)
photocatalyst
to
facilitate
the
direct
coupling
of
aldehydes
with
N-heterocycles
at
ambient
temperature.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
57(5), С. 795 - 813
Опубликована: Фев. 23, 2024
ConspectusThe
selective
functionalization/transformation
of
ubiquitous
pyridine-fused
N-heteroarenes
is
a
practical
method
to
synthesize
structurally
novel
N-heterocycles,
which
important
for
the
development
medicines,
bioactive
agents,
agrochemicals,
materials,
ligands,
sensors,
pigments,
dyes,
etc.
However,
owing
thermodynamic
stability,
kinetic
inertness,
and
lone
electron
pair–induced
catalyst
deactivation
N-heteroarenes,
limited
strategies
(e.g.,
C–H
activation/functionalization,
electrophilic
substitution,
Minisci
reaction)
are
available
realize
synthetic
purpose
maintain
aromaticity
final
products.
Moreover,
relevant
transformations
have
limitations
such
as
needing
harsh
reaction
conditions,
requiring
preinstallation
specific
coupling
agents
containing
transformable
functionalities
or
directing
groups,
using
less
environmentally
benign
oxidants
and/or
acidic
activators,
poor
selectivity.
Herein,
considering
that
imines,
enamines,
radicals,
cyclic
amines
generated
during
reduction
precise
transformation
these
reductive
intermediates
offers
fundamental
basis
developing
tandem
reactions.
Our
group
revealed
slow
rate,
synergistic
catalysis,
controlled
electroreduction
effective
fulfilling
functionalization
N-heteroarenes.
Thus,
we
established
series
new
methods
provide
diverse
construction
modalities
functionalized
N-heterocycles.
The
striking
features
include
high
efficiency,
atom
economy,
use
readily
accessible
feedstocks
in
absence
flammable
pressurized
H2
gas,
alongside
promising
potential
obtained
N-heterocyclic
present
study
would
be
appealing
fields
organic
chemistry,
biomedical
functional
materials.
This
Account
describes
application
dearomatization
substrate-activating
reaction-initiating
modes
summarizes
via
alkylation,
arylation,
annulation
at
nitrogen,
α,
β,
other
remote
carbon
sites
achieved
over
past
8
years.
Details
regarding
reactions
their
plausible
mechanisms
perspectives
discussed.
We
hope
our
contributions
this
field
will
aid
further
tackle
intractable
challenges
area.
