The Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
87(24), P. 16458 - 16472
Published: Nov. 28, 2022
Due
to
the
inert
redox
activity
and
high
triplet
energy,
radical
chemistry
of
1,3-dicarbonyl
compounds
usually
requires
prefunctionalization
substrates,
external
oxidant,
high-energy
UV
light.
Here,
we
report
a
visible-light-driven
photocatalyst/cobaloxime
system
composed
photosensitized
energy
transfer
reaction
(PEnT)
photoinduced
electron
(PET)
with
an
interrupted
6π-photocyclization/dehydrogenative
aromatization
in
one
pot
synthesize
10-phenanthrenols.
Preliminary
mechanistic
studies
revealed
that
fac-Ir(ppy)3
plays
dual
roles
catalysis
for
photocycloaddition
via
1,2-biradical
intermediates
photoredox/cobaloxime
dehydrogenative
1,4-biradical
rather
than
6π
photocyclization
tandem
reaction.
In
contrast
previous
well-established
compounds,
provide
new
strategy
activation
under
visible
light
catalysis,
affording
novel
cyclization
extremely
atom
economy
synthesis
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(34), P. 9055 - 9062
Published: Jan. 1, 2023
We
introduce
a
versatile
Rh(i)-catalyzed
cascade
reaction,
combining
C(sp2)-H
bond
functionalization
and
amidation
between
N-arylphosphanamines
acrylates.
This
innovative
approach
enables
the
rapid
synthesis
of
dihydroquinolinone
scaffolds,
common
heterocycle
found
in
various
pharmaceuticals.
Notably,
presence
phosphorus
atom
facilitates
aniline
ortho-C(sp2)-H
activation
prior
to
N-P
hydrolysis,
streamlining
one-pot
intramolecular
amidation.
Moreover,
we
demonstrate
applicability
this
reaction
by
synthesizing
an
antipsychotic
drug.
Detailed
mechanistic
investigations
revealed
involvement
Rh-H
intermediate,
with
substrate
inhibition
through
catalyst
saturation.
Chinese Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
42(12), P. 4323 - 4323
Published: Jan. 1, 2022
Oxindole
derivatives
are
well
developed
in
many
fields,
and
this
special
heterocyclic
scaffold
is
more
widely
used
natural
products
bioactive
molecules
due
to
its
unique
functionality.Therefore,
it
very
important
explore
new
synthesis
methods
for
motif.A
visible
light-assisted
photocatalyst-free
protocol
the
efficient
of
sulfonylated
oxindoles
under
mild
condition
was
reported.The
present
method
starts
from
simple
readily
available
N-arylacrylamide
sodium
sulfinates,
uses
cheap
K2S2O8
as
oxidant,
features
moderate
good
yields
excellent
functional
group
tolerance.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(13), P. 9094 - 9104
Published: June 14, 2023
A
photocatalyst-
and
additive-free
visible-light-induced
6π-photocyclization
of
ortho-biaryl-appended
β-ketoesters
has
been
developed.
Upon
irradiation
with
visible
light,
substrates
undergo
6-endo-trig
cyclization/1,5-H
shift
to
9,10-dihydrophenanthren-9-ols
high
efficiency
selectivity.
The
reaction
proceeds
via
conrotatory
ring
closure
followed
by
a
suprafacial
1,5-hydrogen
leading
the
observed
single
trans-fused
products.
Preliminary
mechanistic
studies
reveal
feasibility
both
1,5-H
intersystem
crossing
diradical
intermediate.
Organic Chemistry Frontiers,
Journal Year:
2022,
Volume and Issue:
9(22), P. 6156 - 6164
Published: Jan. 1, 2022
A
novel
tandem
photocycloaddition/dehydrogenative
aromatization
with
hydrogen
evolution
of
ortho
biaryl-appended
1,3-dicarbonyl
compounds
for
the
synthesis
10-phenanthrenol
via
cobaloxime
catalysis
is
disclosed.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(7), P. 5060 - 5068
Published: March 25, 2024
Radical
cyclization
has
been
demonstrated
to
be
an
efficient
method
access
functionalized
heterocycles
from
easily
accessible
raw
materials.
Described
herein
is
the
development
of
a
photocatalytic
proton-coupled
electron
transfer
(PCET)
strategy
for
synthesis
isoquinoline-1,3-diones
using
readily
prepared
naphthalimide
(NI)-based
organic
photocatalysts.
The
process
features
free
metal-complex
photocatalysts,
acids,
and
mild
reaction
conditions.
This
radical
protocol
broad
substrate
scope
can
effectively
applied
variety
medicinally
relevant
substrates.
Furthermore,
control
experiments
were
conducted
elucidate
mechanism
this
visible
light-induced
methodology.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(10), P. 2453 - 2458
Published: Jan. 1, 2023
An
efficient
protocol
to
access
phenanthrene-9,9(10
H
)-dicarbonitrile
derivatives
through
visible-light-induced
cyclization
of
2-malononitrilemethylene-substituted
1,1′-biphenyls
under
metal-free
conditions
was
developed.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(22), P. 4014 - 4020
Published: Oct. 10, 2023
Abstract
Chemoselective
cyclizations
of
1,3‐dicarbonyl
compounds
with
hydroxyketones
for
the
selective
formation
two
2,3,5‐trisubstituted
furans
have
been
reported.
While
TsOH‐mediated
cyclization
in
DCM
afforded
2‐acylfurans,
additional
copper
catalyst
acetone
turned
over
selectivity
generation
3‐acylfurans.
The
featured
advantages
both
reactions
include
simple
conditions,
high
yielding,
broad
substrate
scope,
gram
scalability,
and
H
2
O
as
sole
byproduct.
