A
photoredox/nickel
dual
catalysis
is
presented
for
the
construction
of
several
kinds
useful
nitrogen-containing
heterocycles.
This
protocol
regioselective
and
features
a
broad
substrate
scope.
It
provides
direct
access
to
heterocycles
by
reacting
alkyl
chlorides
with
readily
available
activated
unactivated
alkenes.
Moreover,
this
can
be
easily
scalable
gram-scale,
it
feasible
use
sunlight
as
light
source.
Mechanistic
studies
suggest
that
energy
transfer
pathway
involved
in
catalytic
process.
Organic Letters,
Год журнала:
2024,
Номер
26(12), С. 2440 - 2444
Опубликована: Март 19, 2024
An
iodoarene-driven
electroreductive
remote
C(sp3)–H
arylation
of
unsymmetrical
1-(o-iodoaryl)alkyl
ethers
with
cyanoarenes
for
the
site
selective
synthesis
α-(hetero)aryl
is
developed.
With
introduction
as
both
aryl
sources
and
electron
transfer
mediators,
this
method
includes
an
strategy
to
enable
regiocontrollable
formation
two
new
bonds,
one
C(sp2)–H
bond,
C(sp2)–C(sp3)
in
a
single
reaction
step
through
sequence
halogen
atom
(XAT),
hydrogen
(HAT),
radical–radical
coupling,
decyanation.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(3), С. 1703 - 1708
Опубликована: Янв. 16, 2024
Visible-light-induced
three-component
1,2-alkylpyridylation
of
alkenes
with
unactivated
alkyl
iodides
and
aryl
cyanides
is
reported
via
a
photocatalytic
halogen-atom
transfer
(XAT)
strategy.
This
metal-free
protocol
utilizes
readily
available
tertiary
alkylamine
as
the
terminal
reductant
to
smoothly
convert
into
corresponding
carbon
radical
species.
The
reaction
features
broad
substrate
scope,
excellent
functional
group
tolerance,
high
efficiency,
mild
conditions.
practicability
this
methodology
further
demonstrated
in
late-stage
difunctionalization
bioactive
molecules.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(14), С. 3138 - 3143
Опубликована: Май 11, 2024
Abstract
Visible‐light‐induced
difunctionalization
of
alkenes
is
a
powerful
strategy
for
constructing
complex
molecules.
Herein,
we
disclose
three‐component
1,2‐alkylpyridylation
under
mild
and
photosensitizers‐free
conditions.
UV‐vis
absorption
spectroscopy
studies
NMR
titration
experiments
indicate
that
the
formation
an
EDA
between
4‐alkyl‐DHPs
4‐cyanopyridines.
Primary,
secondary,
tertiary
C(
sp
3
)‐centered
radicals
were
formed
by
homolytic
cleavage
4‐alkyl‐DHPs.
Gram‐scale
synthesis
late‐stage
functionalization
medicinally
relevant
molecules
showed
synthetic
potential
our
methodology.
The
β-pyridyl
amide
is
a
critical
scaffold
in
medical
discovery
yet
lacks
efficient
synthetic
methods.
Here,
we
describe,
for
the
first
time,
visible-light-induced,
redox-neutral
radical
cross-coupling
reaction
involving
alkenes,
oxamic
acids,
and
cyanopyridines
that
offers
versatile
assembly
of
β-pyridylamides.
This
approach
features
mild
conditions,
high
step
efficiency,
substrate
breadth,
providing
green
strategy
alkene
pyridyl-carbamoylation.
Achieving
this
transformation
relies
on
catalytic
system,
which
adeptly
avoids
competing
nucleophilic
carbamoyl
with
electrophilic
pyridyl
radical,
enabling
three-component
tandem
process
chemoselectivity.
Aryl
chlorides
are
more
commercially
available
and
lower
cost
compared
with
aryl
bromides
iodides.
However,
the
use
of
(hetero)aryl
as
radical
precursors
for
di(hetero)arylation
alkenes
remains
an
underdeveloped
area.
Furthermore,
existing
examples
theses
reactions
predominantly
confined
to
activated
alkenes.
In
this
study,
we
introduce
a
photoirradiation-promoted
benzophenone-catalyzed
1,2-di(hetero)arylation
process
that
is
applicable
both
unactivated
alkenes,
utilizing
cyanoarenes
sources.
Importantly,
method
allows
simultaneous
introduction
two
heterocycles
high
regioselectivity.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(15), С. 4182 - 4186
Опубликована: Янв. 1, 2024
In
this
paper,
we
developed
an
electro-reductive
aryl-to-alkyl
radical
relay
arylation
reaction
of
a
remote
C(sp
3
)–H
bond
via
1,5-HAT
process.
This
protocol
features
mild
conditions,
simple
operation,
and
broad
substrate
scope.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(18), С. 13641 - 13653
Опубликована: Сен. 5, 2024
We
report
a
visible
light-induced
photoreductive
strategy
for
three-component
diarylation
of
alkenes
with
aryl
halides
and
cyanoaromatics.
Upon
photoredox
catalysis
tertiary
alkyl
amines
as
the
electron
transfer
agent,
selectively
undergo
halogen
atom
to
generate
radicals
two
C(sp
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
22(31), С. 6370 - 6375
Опубликована: Янв. 1, 2024
Visible-light-induced
three-component
1,2-alkyl-arylation
of
alkenes
and
alkyl
radical
addition/cyclization
acrylamides
have
been
realized
using
a
photocatalytic
halogen-atom
transfer
(XAT)
strategy.
