Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(2), P. 467 - 472
Published: Jan. 5, 2024
Disclosed
here
is
a
visible-light
photoredox-catalyzed
intermolecular
sequential
α-aminomethyl/carboxylative
dearomatization
of
indoles
with
CO2
and
α-aminoalkyl
radical
precursors,
affording
series
functionalized
indoline-3-carboxylic
acids
lactams
in
good
yields
high
regioselectivity.
This
multicomponent
reaction
provides
green
facile
method
for
the
synthesis
diverse
indolines
by
using
as
carboxylic
carbonyl
source.
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(48), P. 14213 - 14225
Published: Jan. 1, 2022
This
Perspective
outlines
the
myriad
of
products
that
can
be
obtained
by
dearomatisation
and
functionalization
heteroarene
substrates.
Complex
3D
molecules
often
prepared
in
one
step
from
simple
arene
starting
materials.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(30)
Published: May 18, 2023
The
rapid
preparation
of
complex
three-dimensional
(3D)
heterocyclic
scaffolds
is
a
key
challenge
in
modern
medicinal
chemistry.
Despite
the
increased
probability
clinical
success
for
small
molecule
therapeutic
candidates
with
3D
complexity,
new
drug
targets
remain
dominated
by
flat
molecules
due
to
abundance
coupling
reactions
available
their
construction.
In
principle,
heteroarene
hydrofunctionalization
offer
an
opportunity
transform
readily
accessible
planar
into
more
three-dimensionally
analogs
through
introduction
single
molecular
vector.
Unfortunately,
dearomative
limited.
Herein,
we
report
strategy
enable
hydrocarboxylation
indoles
and
related
heterocycles.
This
reaction
represents
rare
example
that
meets
numerous
requirements
broad
implementation
discovery.
transformation
highly
chemoselective,
scope,
operationally
simple,
amenable
high-throughput
experimentation
(HTE).
Accordingly,
this
process
will
allow
existing
libraries
heteroaromatic
compounds
be
translated
diverse
exploration
classes
medicinally
relevant
molecules.
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.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: Aug. 5, 2022
Reactions
that
lead
to
destruction
of
aromatic
ring
systems
often
require
harsh
conditions
and,
thus,
take
place
with
poor
selectivities.
Selective
partial
dearomatization
fused
arenes
is
even
more
challenging
but
can
be
a
strategic
approach
creating
versatile,
complex
polycyclic
frameworks.
Herein
we
describe
general
organophotoredox
for
the
chemo-
and
regioselective
structurally
diverse
aromatics,
including
quinolines,
isoquinolines,
quinoxalines,
naphthalenes,
anthracenes
phenanthrenes.
The
success
method
chemoselective
oxidative
rupture
moieties
relies
on
precise
manipulation
electronic
nature
arenes.
Mechanistic
studies
show
addition
hydrogen
atom
transfer
(HAT)
agent
helps
favor
pathway
over
thermodynamically
downhill
aromatization
pathway.
We
this
strategy
applied
rapid
synthesis
biologically
valued
targets
late-stage
skeletal
remodeling
en
route
structures.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(18), P. 10314 - 10321
Published: April 26, 2023
Samarium
diiodide
(SmI2)
mediated
reductive
coupling
reactions
are
powerful
methods
for
the
construction
of
carbon-carbon
bond
in
organic
synthesis.
Despite
extensive
development
recent
decades,
successful
examples
corresponding
asymmetric
remained
scarce,
probably
due
to
involvement
highly
reactive
radical
intermediates.
In
this
Article,
we
report
an
enantioselective
dearomatization
indoles
via
SmI2-mediated
intermolecular
with
ketones.
The
utilization
samarium
reductant
supported
by
chiral
tridentate
aminodiol
ligands
allows
facile
synthesis
indoline
molecules
bearing
two
contiguous
stereogenic
centers
high
yields
(up
99%)
and
stereoselectivity
99:1
er
>20:1
dr).
Combined
experimental
computational
investigations
suggested
that
parallel
single-electron
transfer
each
substrate
from
radical-radical
recombination
manner,
which
is
a
unique
mechanistic
scenario
reactions.
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.
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
28(56)
Published: July 9, 2022
We
report
herein
a
convenient
and
scalable
dearomative
hydroacylation
reaction
of
indoles.
Employing
readily
available
aldehydes
as
the
acyl
source
TBADT
an
inexpensive
direct
HAT
photocatalyst,
variety
indoles
derivatives
were
converted
into
synthetically
interesting
2-acylindolines
in
good
to
excellent
yields
well
great
diastereoselectivity
under
mild
conditions.
An
asymmetric
version
was
successfully
developed
experimental
mechanistic
investigation
carried
out
order
gain
further
insights
on
assumed
pathway.
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.
