Enantioselective Synthesis of Indole-Fused Polycycles Bearing Four Consecutive Stereocenters via Rhodium Catalysis
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 3, 2025
Indole-fused
polycycles
are
common
in
natural
products
and
bioactive
molecules,
yet
their
concise
efficient
synthesis
remains
challenging,
especially
for
compounds
with
multiple
stereocenters.
Herein,
we
report
the
application
of
a
chiral
CpxRhIII
catalyst
enantioselective
C–H
activation/[4+2]
annulation
indoles
bicyclic
alkenes.
This
catalytic
system
exhibits
high
enantioselectivity
broad
functional
group
tolerance
operates
under
benign
conditions.
The
scope
this
methodology
encompasses
variety
substrates,
delivering
novel
polycyclic
four
consecutive
stereocenters
bridged
ring
good
to
excellent
yields
remarkable
enantioselectivities
(≤1:99
er).
approach
facilitates
structurally
diverse
molecules
that
retain
integrity
while
introducing
chirality.
More
importantly,
3ab
significantly
inhibited
proliferation
CESS
Kasumin-1
cells
IC50
values
0.76
0.28
μM,
respectively.
In
addition,
has
been
demonstrated
as
an
effective
agent
promoting
apoptosis
cells.
Язык: Английский
Asymmetric Intramolecular Amination Catalyzed with Cp*Ir-SPDO via Nitrene Transfer for Synthesis of Spiro-Quaternary Indolinone
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(28), С. 18841 - 18847
Опубликована: Июль 8, 2024
An
asymmetric
intramolecular
spiro-amination
to
high
steric
hindering
Язык: Английский
Enantioselective Nitrene Transfer to Hydrocinnamyl Alcohols and Allylic Alcohols Enabled by Systematic Exploration of the Structure of Ion-Paired Rhodium Catalysts
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(32), С. 22629 - 22641
Опубликована: Июль 31, 2024
This
work
describes
highly
enantioselective
nitrene
transfer
to
hydrocinnamyl
alcohols
(benzylic
C–H
amination)
and
allylic
(aziridination)
using
ion-paired
Rh
(II,II)
complexes
based
on
anionic
variants
of
Du
Bois'
esp
ligand
that
are
associated
with
cinchona
alkaloid-derived
chiral
cations.
Directed
by
a
substrate
hydroxyl
group,
our
previous
these
had
not
been
able
achieve
high
enantioselectivity
most
useful
short-chain
compounds,
we
overcame
this
challenge
through
combination
catalyst
design
modified
conditions.
A
hypothesis
modulation
the
linker
between
sulfonate
group
central
arene
spacer
might
provide
better
fit
for
shorter
chain
length
substrates
led
development
new
biaryl-containing
scaffold,
which
has
allowed
broad
scope
both
classes
be
realized
first
time.
Furthermore,
describe
systematic
structural
"knockout"
study
cation
elucidate
features
crucial
enantioinduction.
De
novo
synthesis
scaffolds
surprising
finding
ee
quinoline
nitrogen
alkaloid
is
crucial,
although
its
location
within
heterocycle
could
varied,
even
leading
superior
catalyst.
The
free
also
should
possess
naturally
occurring
diastereomeric
configuration
alkaloid.
These
findings
underline
privileged
nature
scaffold
insight
into
how
cations
used
in
other
catalysis
contexts.
Язык: Английский
Water-Mediated Radical Kinetic Resolution of Terminal Activated N-Carbamate Aziridines
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 7, 2025
Optically
active
terminal
aziridines
are
fundamental
building
blocks
for
constructing
complex
nitrogen-containing
molecules.
Notably,
the
protecting
group
on
amino
moiety
critically
governs
not
only
reactivity
and
enantioselectivity
during
aziridine
formation
but
also
efficiency
of
downstream
functionalization.
While
carbamates
among
most
widely
employed
groups
in
amine-related
synthesis
due
to
their
versatility
orthogonality,
enantioselective
incorporation
into
remains
a
long-standing
challenge.
Herein,
we
present
first
radical
approach
kinetic
resolution
aziridines,
enabling
efficient
access
broad
range
bearing
diverse
carbamate
substituents.
This
transformation
exploits
dual
functionality
dinuclear
titanium
catalyst,
which
enables
enantiodiscriminative
activation
racemic
coordinative
H2O
as
sustainable
hydrogen-atom
donor.
Mechanistic
studies
reveal
that
optimal
distribution
catalyst
between
is
crucial
sustaining
cooperative
catalytic
cycle.
Язык: Английский
Synthesis of N–H Aziridines from Unactivated Olefins Using Hydroxylamine-O-Sulfonic Acids as Aminating Agent
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(9), С. 6263 - 6273
Опубликована: Апрель 23, 2024
Herein,
we
presented
a
practical
methodology
for
the
intermolecular
aziridination
of
alkenes,
using
HOSA
as
aminating
agent,
alongside
pyridine
or
piperidine
base,
within
HFIP
solvent
system.
Notably,
this
approach
showcases
excellent
reactivity,
especially
with
nonactivated
and
facilitates
transformation
various
alkenes
substrates,
including
mono-,
di-,
tri,
tetra-substituted
into
aziridines
moderate
to
yield.
This
method
presents
promising
avenue
synthesizing
from
wide
range
featuring
benefits
straightforward
operation,
mild
reaction
conditions,
extensive
substrate
compatibility,
scalability.
Язык: Английский
Metal-Free Aziridination of Unactivated Olefins via Transient N-Pyridinium Iminoiodinanes
JACS Au,
Год журнала:
2024,
Номер
4(11), С. 4187 - 4193
Опубликована: Окт. 10, 2024
We
describe
a
metal-free
aziridination
of
unactivated
olefins
to
generate
Язык: Английский
Synthesis of Cyclohexenone(aryl)iodonium Salts and Their Application in Construction of Fused aza‐Heterocyclic Skeletons
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(21), С. 4462 - 4469
Опубликована: Июль 23, 2024
Abstract
A
class
of
cyclohexenone(aryl)iodonium
salts
was
readily
prepared
from
2‐iodocyclohexenones
and
arenes
under
mild
conditions.
This
novel
series
hypervalent
iodonium
building
blocks
exhibits
dual
characteristics
hyperiodonium
α,β‐unsaturated
cyclic
ketones,
enabling
access
to
intricate
aza‐heterocycles.
The
reaction
these
with
arylamines
or
aryl
sulfonamides
affords
2‐acylaziridines,
while
2‐aminobenzimidazoles
2‐aminoimidazoles
leads
the
formation
1
H
‐imidazo[1,2‐
a
]imidazole‐fused
compounds.
transformation
is
postulated
proceed
through
an
exclusive
hyperiodonium‐mediated
N
‐Michael
addition
followed
by
‐annulation
cascade.
Язык: Английский
Transition‐Metal Catalyzed Enantioselective Aziridination Reaction: Recent Development in Catalysis and Future Perspectives
ChemCatChem,
Год журнала:
2024,
Номер
16(21)
Опубликована: Июль 16, 2024
Abstract
Chiral
aziridines
are
important
motifs
in
natural
products
and
biologically
significant
compounds,
as
well
one
of
the
most
valuable
versatile
building
blocks
for
construction
diverse
chiral
functionalized
amines.
Because
importance
aziridines,
various
novel
transition‐metal‐based
catalytic
systems
synthetic
strategies
have
been
established
to
investigate
highly
effective
enantioselective
aziridination
process.
This
review
outlined
recent
advances
made
transition‐metal
catalyzed
reactions,
challenges
potential
field
at
current
stage.
Язык: Английский
Rhodium-catalyzed atropodivergent hydroamination of alkynes by leveraging two potential enantiodetermining steps
Science Advances,
Год журнала:
2024,
Номер
10(48)
Опубликована: Ноя. 27, 2024
A
pair
of
enantiomers
is
known
to
have
different
biological
activities.
Two
catalysts
with
opposite
chirality
are
nearly
always
required
deliver
both
enantiomeric
products.
In
this
work,
chiral
rhodium(III)
cyclopentadienyl
complexes
repurposed
as
efficient
for
enantiodivergent
and
atroposelective
hydroamination
sterically
hindered
alkynes.
Products
been
obtained
using
the
same
or
closely
analogous
catalyst
in
good
efficiency
excellent
enantioselectivity,
enantiodivergence
was
mainly
enabled
by
an
achiral
carboxylic
acid
its
silver
salt.
Mechanistic
studies
revealed
origin
ascribable
switch
enantiodetermining
step
(alkyne
insertion
versus
protonolysis)
under
control,
which
constitutes
a
previously
unidentified
working
mode
leveraging
two
elementary
steps.
Язык: Английский
Synthetic Approaches for the Construction of Chiral Aziridines
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 30, 2024
Abstract
Optically
active
aziridines
represent
a
pivotal
class
of
rigid
three‐membered
nitrogen‐heterocyclic
compounds
found
in
natural
products,
pharmaceuticals,
agrochemicals,
and
functional
motifs,
which
have
demonstrated
outstanding
practicability
as
therapeutic
molecular
frameworks,
versatile
synthetic
endpoints,
materials
both
academic
industrial
communities.
Recent
years
witnessed
broad
spectrum
prominent
breakthroughs
the
field
chiral
due
to
aziridine‐based
three‐dimensional
pharmacophores,
resulted
streamlining
drug
discovery
process.
Over
past
few
decades,
particular
attention
has
been
directed
towards
strategically
efficient,
versatile,
practical
assembly
optically
aziridines.
These
synthesis
approaches
great
potential
context
construction
pharmaceutical
molecules,
biologically
pharmacologically
relevant
materials.
In
this
review,
several
strategies
for
are
summarized,
could
be
divided
into
five
categories:
(1)
Introduction;
(2)
Construction
via
reactions
olefines
with
nitrene
sources;
(3)
imines
carbenes;
(4)
reaction
azirines;
(5)
intramolecular
cyclization
amine
derivatives.
Язык: Английский