The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 6, 2025
The
synthesis
of
valuable
2a,3-dihydrobenzo[cd]indolines
was
successfully
achieved
by
combining
IPr-Pdcycle-OxaNaphthyl-catalyzed
cross-coupling
and
proton-induced
hydroarylation
in
a
one-pot
method.
In
situ-generated
alkynyl-functionalized
3,3-disubstituted
indolines
were
proved
as
the
key
intermediate,
bearing
broad
scope
substrates
with
diverse
functional
groups
electronic
properties.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 23, 2024
Abstract
Catalytic
enantioselective
preparation
of
alkene
atropisomers
with
multiple
stereogenic
elements
and
discovery
their
applications
have
become
significant
but
challenging
issues
in
the
scientific
community
due
to
unique
structures
this
class
atropisomers.
We
herein
report
first
catalytic
atroposelective
cyclopentenyl[
b
]indoles,
a
new
kind
atropisomers,
point
axial
chirality
via
an
unusual
rearrangement
reaction
3‐indolylmethanols
under
asymmetric
organocatalysis.
Notably,
novel
type
promising
developing
chiral
ligands
or
organocatalysts,
discovering
antitumor
drug
candidates
fluorescence
imaging
materials.
Moreover,
theoretical
calculations
elucidated
possible
mechanism
non‐covalent
interactions
control
enantioselectivity.
This
approach
offers
synthetic
strategy
for
elements,
represents
3‐indolylmethanols,
which
will
advance
chemistry
indole
chemistry.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 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.
Chemical Synthesis,
Год журнала:
2023,
Номер
3(1), С. 6 - 6
Опубликована: Янв. 1, 2023
In
recent
years,
it
has
become
an
urgent
task
to
design
new
types
of
indole-based
platform
molecules
for
Nazarov-type
cyclizations
and
develop
organocatalytic
synthesizing
indole
derivatives.
To
fulfill
this
task,
in
work,
by
changing
the
alkynyl
terminal
substituent
from
t-Bu
aryl
group,
reactivity
3-alkynyl-2-indolylmethanols
is
modulated
serve
as
competent
substrates
Brønsted
acid-catalyzed
cyclization.
Based
on
reactivity,
first
cyclization
aryl-substituted
with
2-naphthols
accomplished,
leading
efficient
construction
a
class
axially
chiral
3,
4-dihydrocyclopenta[b]indole
scaffolds.
This
preliminary
investigation
asymmetric
provides
optional
strategy
atroposelective
cyclopenta[b]indole
addition,
preparation
optical
purity
established
through
resolution,
which
could
complementary
method
catalytic
approaches.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(3)
Опубликована: Ноя. 28, 2023
Abstract
Indole‐based
planar‐chiral
macrocycles
are
widely
found
in
natural
products
and
bioactive
molecules.
However,
sharp
contrast
to
the
preparation
of
indole‐based
axially
chiral
structures,
enantioselective
catalysis
is
still
a
formidable
task
so
far.
Here
we
report
an
N
‐heterocyclic
carbene
(NHC)‐catalyzed
intramolecular
atroposelective
macrocyclization
3‐carboxaldehyde
indole/pyrroles,
featuring
with
broad
substrate
scope
good
functional
group
tolerance,
allowing
for
rapid
access
diverse
indole/pyrrole‐based
various
tether‐lengths
(10–16
members)
yields
excellent
enantioselectivities.
Importantly,
macrocyclic
structures
both
planar
axial
chirality
were
directly
efficiently
obtained
through
this
protocol
enantioselectivities
diastereoselectivities.
In
addition,
these
synthesized
offer
many
possibilities
chemists
develop
new
catalysts
or
ligands,
as
well
reactions.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(13), С. 1474 - 1480
Опубликована: Март 1, 2024
Comprehensive
Summary
The
privileged
C
2
‐symmetric
rigid
phenol‐type
ligand
is
more
attractive
but
challenging
in
asymmetric
catalysis.
Herein,
we
designed
and
synthesized
a
class
of
rigid‐featured
chiral
tridentate
Phenol‐2NO
ligands,
that
incorporate
the
advantages
both
phenol
skeleton
pyrroloimidazolone‐based
N
‐oxide
moiety,
from
readily
available
L
‐prolinamides
operationally
simple
two
steps
up
to
44%
overall
yield.
More
importantly,
using
an
achiral
quinoline
derivative
as
additive,
newly
developed
could
serve
anioic
upon
deprotonative
activation
coordinate
Zn(II)
form
highly
enantioselective
catalyst
for
Michael‐type
Friedel‐Crafts
alkylation
reaction
indoles
with
2,3‐dioxopyrrolidines.
Excellent
yields
(up
90%)
high
enantioselectivities
99%
ee)
are
obtained
wide
range
substrates
under
mild
conditions.
Experiments
DFT
calculations
revealed
mechanism
origins
enantioselectivity.
This
also
represented
first
ligand/metal
complex
by
organic
base
additive
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(14), С. 3662 - 3668
Опубликована: Янв. 1, 2023
With
the
aid
of
chiral
phosphoric
acid,
enantioselective
1,6-addition
tryptamines
to
in
situ
formed
alkynyl
7-methylene-7
H
-indoles
from
tertiary
α-(7-indolyl)methanols
has
been
established,
furnishing
axially
tetrasubstituted
allenes
high
yields.
New Journal of Chemistry,
Год журнала:
2024,
Номер
48(4), С. 1688 - 1695
Опубликована: Янв. 1, 2024
This
work
diversified
the
Py-2NO
ligand
library
recently
developed
by
our
group
and
further
expanded
application
of
chiral
ligands
in
asymmetric
catalysis.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(29)
Опубликована: Май 3, 2024
The
chemistry
of
quinone
methides
formed
in
situ
has
been
flourishing
recent
years.
In
sharp
contrast,
the
development
and
utilization
biphenyl
are
rare.
this
study,
we
achieved
a
remote
stereocontrolled
1,12-conjugate
addition
for
first
time.
presence
suitable
chiral
phosphoric
acid,
alkynyl
were
generated
from
α-[4-(4-hydroxyphenyl)phenyl]propargyl
alcohols,
followed
by
enantioselective
with
indole-2-carboxylates.
strategy
enabled
alcohols
to
serve
as
efficient
allenylation
reagents,
providing
practical
access
broad
range
axially
allenes
bearing
(1,1'-biphenyl)-4-ol
unit,
which
previously
less
accessible.
Combined
control
experiments,
density
functional
theory
calculations
shed
light
on
reaction
mechanism,
indicating
that
enantioselectivity
originates
nucleophilic
methides.
Notably,
not
only
versatile
intermediates
was
confirmed
but
also
organocatalytic
1,12-addition
established.
