The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(16), P. 11716 - 11726
Published: July 27, 2024
We
present
here
a
new
method
for
the
synthesis
of
2-substituted-3-aryl
benzoheterocycles
through
more
challenging
constrained
[1,5]-type
Friedel–Crafts
reaction/rearrangement
and
aromatization
process.
By
using
readily
available
2-aryoxy-1,3-indandiones
2-arylamino-1,3-indandiones,
range
benzofurans
indoles
were
prepared
in
good
to
excellent
yields
(yields
up
86%)
under
catalysis
CF3SO3H
or
Sm(OTf)3.
Compared
with
previous
methods
constructing
similar
structures,
this
approach
offers
several
advantages,
including
use
easily
accessible
starting
materials,
mild
reaction
conditions,
high
yield,
regio-
diastereoselectivity,
broad
substrate
scope.
Science Advances,
Journal Year:
2024,
Volume and Issue:
10(19)
Published: May 10, 2024
Atropisomeric
indoles
defined
by
a
N─N
axis
are
an
important
class
of
heterocycles
in
synthetic
and
medicinal
chemistry
material
sciences.
However,
they
remain
heavily
underexplored
due
to
limited
methods
challenging
stereocontrol
over
the
short
bonds.
Here,
we
report
highly
atroposelective
access
axially
chiral
via
asymmetric
Larock
reaction.
This
protocol
leveraged
powerful
role
phosphoramidite
ligand
attenuate
common
dissociation
original
reaction,
forming
with
excellent
functional
group
tolerance
high
enantioselectivity
palladium-catalyzed
intermolecular
annulation
between
readily
available
o
-iodoaniline
alkynes.
The
multifunctionality
prepared
allowed
diverse
post-coupling
transformations,
affording
broad
array
functionalized
indoles.
Experimental
computational
studies
have
been
conducted
explore
reaction
mechanism,
elucidating
enantio-determining
rate-limiting
steps.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(42), P. 29214 - 29223
Published: Oct. 9, 2024
Macrocycles
incorporating
conformationally
defined
indoles
are
widely
found
in
bioactive
natural
products.
However,
the
catalytic
enantioselective
synthesis
of
planar-chiral
via
indolization
involving
macrocyclization
remains
elusive.
Herein,
we
present
first
rhodium(III)-catalyzed
atroposelective
macrocyclization,
which
involves
C-H
activation
aniline,
and
a
subsequent
oxidation
[3
+
2]
annulation
reaction
with
an
intramolecular
alkyne.
This
protocol
achieves
construction
indoles,
planar
chirality
control
single
step.
Importantly,
this
strategy
produces
macrocyclic
atropisomers
bearing
full-carbon
ansa
chains,
represent
challenging
targets
organic
synthesis.
Thermodynamic
experiments
revealed
that
rotational
barrier
chain-linked
atropisomer
was
lower
than
oxa-ansa
chain.
The
mechanism
elucidated
by
computational
studies,
alkyne
insertion
steps
collectively
determined
enantioselectivity.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 20, 2025
Lewis
acid-enabled
reactions
of
donor-acceptor
cyclopropanes
(DACs)
with
indoline-2-thiones
are
reported.
The
reaction
exhibits
tunable
annulation
depending
on
the
acid
and
substituent
at
N1
indoline-2-thiones.
With
AlCl3
as
1-isopropylindoline-2-thiones
reactants,
a
direct
ring
opening
DACs,
followed
by
intramolecular
nucleophilic
addition/dehydration
takes
place
leading
to
formation
dihydro-2H-thiepino[2,3-b]indoles
in
moderate
good
yields.
Using
Yb(OTf)3
promoter
1-unsubstituted
(3
+
2)
cycloaddition
DACs
accompanied
sulfur
rearrangement
give
3-indolyl-4,5-dihydrothiophenes
In
addition,
synthetic
transformation
3-indolyl-4,5-dihydrothiophene
sulfone
indole-based
axially
chiral
scaffolds
further
extends
utility
structural
complexity.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 24, 2025
Here
we
present
an
enantioselective
intramolecular
hydroamination
reaction
of
o-aminophenyl-1,3-enynes
via
cooperative
catalysis
Pd(0)
and
chiral
phosphoric
acid.
This
approach
enables
the
efficient
construction
N–N/C–N
axially
stereogenic
indoles
with
broad
skeletal
diversity
high
levels
enantioselectivity
in
a
completely
atom-economic
manner.
Mechanistic
studies
indicate
that
protonation
alkyne
moiety
π-Lewis
base
activation
is
favored,
phosphate
counteranion
plays
crucial
role
controlling
atroposelectivity
ring-closure
step.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Jan. 22, 2025
Abstract
The
enantioselective
domino
Heck/cross-coupling
has
emerged
as
a
powerful
tool
in
modern
chemical
synthesis
for
decades.
Despite
significant
progress
relative
rigid
skeleton
substrates,
the
implementation
of
asymmetric
cascades
highly
flexible
haloalkene
substrates
remains
challenging
and
long-standing
goal.
Here
we
report
an
efficient
Heck/Tsuji−Trost
reaction
vinylic
halides
with
1,3-dienes
enabled
by
palladium
catalysis.
Specifically,
Heck
insertion
stereodetermining
step
to
form
ƞ
3
allyl
complex
situ
trapping
nucleophiles
enable
Heck/etherification
formal
(4
+
2)
cycloaddition
manner.
Engineering
Sadphos
bearing
androgynous
non-C
2
-symmetric
chiral
sulfinamide
phosphine
ligands
are
vital
component
achieving
excellent
catalytic
reactivity
enantioselectivity.
This
strategy
offers
general,
modular
divergent
platform
rapidly
upgrading
feedstock
dienes
various
value-added
molecules
is
expected
inspire
development
other
Heck/cross-couplings.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 11, 2025
A
novel
P(═O)R2-directed
asymmetric
catalytic
olefination
has
been
developed,
enabling
efficient
access
to
carbon–nitrogen
axially
chiral
products
with
excellent
yields
(up
92%)
and
enantioselectivity
99%
enantiomeric
excess).
The
synergistic
coordination
of
phosphine
oxide
functionality
l-pGlu-OH
the
Pd
metal
center,
serving
as
an
directing
group
ligand,
was
key
success
this
C–H
functionalization
system.
reaction
demonstrated
a
broad
substrate
scope,
yielding
33
distinct
C–N
axial
products.
absolute
configuration
unambiguously
confirmed
via
X-ray
diffraction
analysis.
Additionally,
three
representative
applications
were
showcased,
involving
reduction
oxidation
produce
phosphines
related
derivatives.
plausible
cycle
mechanism
proposed,
supported
by
detailed
experimental
studies.
Aggregates
in
system
identified
aggregation-induced
polarization
experiments.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 24, 2025
The
indole
skeleton
exists
widely
in
natural
products,
pharmaceuticals,
and
materials.
We
disclose
here
a
trifluoromethyl
group
induced
regioselective
Larock
synthetic
method
from
unsymmetric
2-CF3-1,3-enynes.
presence
of
is
determinable
for
the
regioselectivity.
Once
CF3
was
replaced
with
methyl
or
phenyl
group,
ratio
1:1
to
1:1.4
isomers
were
obtained.
This
strategy
features
good
regioselectivity,
broad
substrate
scope,
high
functional
tolerance.
protocol
reported
offers
an
alternative
solution
rare
3,4-functionalization
products
further
transformed
show
distinctive
reactivity
hydroboration–oxidation
hydro-bromination.
Catalysts,
Journal Year:
2025,
Volume and Issue:
15(4), P. 320 - 320
Published: March 27, 2025
Axially
chiral
structures
have
become
increasingly
common
in
modern
materials
and
pharmaceuticals,
especially
as
ligands
organocatalysts,
highlighting
their
growing
significance.
In
the
field
of
pharmaceutical
research,
there
are
several
notable
examples
worth
highlighting,
such
antibiotics
vancomycin,
Knipholone,
Mastigophorene
A.
Over
past
decade,
availability
axially
compounds
has
significantly
improved
through
advancements
existing
strategies
introduction
catalytic
atroposelective
synthesis
concepts.
These
synthetic
not
only
broaden
scope
chemical
reactions,
but
also
facilitate
construction
frameworks
with
high
application
value.
Currently,
various
methods
available
for
achieving
stereoselective
under
catalyst
control,
including
desymmetrization,
(dynamic)
kinetic
resolution,
cross-coupling
de
novo
ring-forming
synthesis.
This
paper
focuses
on
recent
advances
constructing
atropisomers
palladium-catalyzed
asymmetric
cyclization
strategies.
