Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(20), P. 4228 - 4237
Published: Aug. 14, 2024
Abstract
A
visible‐light
triplet
photocatalyst
5‐acetyl‐2‐mercapto‐benzoic
acid
methyl
ester
(AcBSH)
was
developed
through
introducing
acetyl
into
benzenethiolate
to
improve
the
efficiency
of
intersystem
crossing
(ISC)
and
using
o
‐methoxyformyl
increase
molar
extinction
coefficient.
In
photocatalytic
system
AcBSH,
reductive
dearomatization
N
‐arylformylindoles
is
achieved
afford
desired
indolines
in
moderate
excellent
yields,
including
both
indoles
without
(
1
)
with
2‐substituent
2
).
The
a
steric
hindrance
for
conjugation
between
benzoyl
indole
moiety,
makes
exhibit
different
reduction
potentials
E
red
energy
levels
ΔE
T
Thereby,
two
kinds
substrates
undergo
primarily
pathways:
i)
successive
SET/protonation
pathway,
which
merging
photosensitization
via
triplet‐triplet
transfer
(EnT)
photoinduced
SET
,
ii)
single
electron
(SET)
from
concerted
hydrogen
atom
(HAT)
process
.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(9)
Published: Nov. 14, 2023
Visible
light-induced
Pd
catalysis
has
emerged
as
a
promising
subfield
of
photocatalysis.
The
hybrid
nature
radical
species
enabled
wide
array
radical-based
transformations
otherwise
challenging
or
unknown
via
conventional
chemistry.
In
parallel
to
the
ongoing
pursuit
alternative,
readily
available
precursors,
notable
discoveries
have
demonstrated
that
photoexcitation
can
alter
not
only
oxidative
addition
but
also
other
elementary
steps.
This
Minireview
highlights
recent
progress
in
this
area.
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(12), P. 6600 - 6624
Published: Jan. 1, 2024
Dearomatization
has
emerged
as
a
powerful
tool
for
rapid
construction
of
3D
molecular
architectures
from
simple,
abundant,
and
planar
(hetero)arenes.
The
field
evolved
beyond
simple
dearomatization
driven
by
new
synthetic
technology
development.
With
the
renaissance
photocatalysis
expansion
activation
mode,
last
few
years
have
witnessed
impressive
developments
in
innovative
photochemical
methodologies,
enabling
skeletal
modifications
dearomatized
structures.
They
offer
truly
efficient
useful
tools
facile
highly
complex
structures,
which
are
viable
natural
product
synthesis
drug
discovery.
In
this
review,
we
aim
to
provide
mechanistically
insightful
overview
on
these
innovations
based
degree
alteration,
categorized
into
dearomative
functionalization
editing,
highlight
their
utilities.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(22)
Published: April 16, 2024
Abstract
In
this
study,
we
present
an
efficient
and
straightforward
dearomative
hydroalkylation
of
indoles.
By
utilizing
alkanes
or
ethers
as
alkyl
radical
sources
employing
TBADT
a
cost‐effective
photocatalyst
for
direct
hydrogen
atom
transfers
(HAT),
achieved
successful
conversion
these
heterocyclic
derivatives
into
2‐alkylindolines
with
good
to
excellent
yields
high
diastereoselectivity
under
mild
reaction
conditions.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: June 30, 2023
Abstract
Prenylated
and
reverse-prenylated
indolines
are
privileged
scaffolds
in
numerous
naturally
occurring
indole
alkaloids
with
a
broad
spectrum
of
important
biological
properties.
Development
straightforward
stereoselective
methods
to
enable
the
synthesis
structurally
diverse
prenylated
indoline
derivatives
is
highly
desirable
challenging.
In
this
context,
most
direct
approaches
achieve
goal
generally
rely
on
transition-metal-catalyzed
dearomative
allylic
alkylation
electron-rich
indoles.
However,
electron-deficient
indoles
much
less
explored,
probably
due
their
diminished
nucleophilicity.
Herein,
photoredox-catalyzed
tandem
Giese
radical
addition/Ireland–Claisen
rearrangement
disclosed.
Diastereoselective
prenylation
reverse-prenylation
proceed
smoothly
under
mild
conditions.
An
array
tertiary
α-silylamines
as
precursors
readily
incorporated
2,3-disubstituted
high
functional
compatibility
excellent
diastereoselectivity
(>20:1
d.r.).
The
corresponding
transformations
secondary
provide
biologically
lactam-fused
one-pot
synthesis.
Subsequently,
plausible
photoredox
pathway
proposed
based
control
experiments.
preliminary
bioactivity
study
reveals
potential
anticancer
property
these
appealing
indolines.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(25), P. 4720 - 4724
Published: June 20, 2023
Herein,
a
novel
and
expedient
method
was
established
for
the
synthesis
of
polyarylfuran
derivatives.
The
coupling
allenylphosphine
oxide
bromophenol
or
bromonaphthol
enabled
by
visible
light
palladium
catalysis
directly
furnishes
skeletons,
which
involves
radical
tandem
cyclization
cascade
C(sp3)-P(V)
bond
cleavage.
This
protocol
features
easy
operation,
broad
substrate
scope,
high
step
economy,
affording
polyarylfurans
in
moderate
to
good
yields.
Organic Chemistry Frontiers,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
1,4-difunctionalization
of
nonactivated
arenes
has
been
accomplished
by
the
excited-palladium
catalysis
via
radical
generation
a
cyclohexadienyl-Pd(
ii
)
intermediate.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(7), P. 1633 - 1642
Published: Jan. 1, 2023
A
visible
light-driven
dearomatization
of
an
N
-(
o
-haloarylformyl)indole
in
electron
donor–acceptor
(EDA)
complex
with
a
thiophenol.
The
radical
reaction
is
terminated
by
concerted
hydrogen
atom
transfer
(HAT).
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(3), P. 471 - 476
Published: Jan. 13, 2023
A
solvent
(2,2,2-trifluoroethanol
(TFE)
vs
ethyl
alcohol
(EtOH))
switched
synthesis
of
quinolines
and
pyridines
is
illustrated
from
(E)-2-(1,3-diphenylallylidene)malononitriles
via
a
Pd(II)-catalyzed
photochemical
process.
The
active
catalyst
[L2Pd(0)]
generated
serves
as
an
exogenous
photosensitizer.
process
offers
predominantly
Z-alkenylated
in
TFE
EtOH,
respectively.
Furthermore,
large-scale
few
interesting
post-synthetic
modifications
have
been
demonstrated.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(51), P. 9386 - 9391
Published: Dec. 16, 2022
Herein,
we
describe
a
methodology
to
construct
polycyclic
pyrrolophenanthridones
with
an
(amino)alkyl
side
chain
that
involves
visible-light-induced
decarboxylative
radical
addition
for
the
intermolecular
dearomatization
of
indoles
and
subsequent
photoinduced
C(sp2)-X
bond
activation
via
photoexcited
ketones
intramolecular
cyclization
cascade.
Carboxylic
acids
serve
both
as
source
toward
indole
reductants
initiate
electron
transfer
N-acylindole
derivatives
in
reaction
pyrrolophenantridone
skeletons,
which
occurs
under
mild
conditions
good
functional
group
tolerance.
