Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(42), P. 9079 - 9084
Published: Oct. 15, 2024
We
report
a
novel
halogen-bond-assisted
NHC-catalyzed
(dynamic)
kinetic
resolution
strategy
for
the
synthesis
of
axially
chiral
heterobiaryls.
A
class
quinolines
are
prepared
efficiently
in
excellent
enantioselectivities
(≤98%
ee)
employing
3-5
mol
%
NHC
catalyst.
Mechanistic
studies
reveal
indispensability
5-bromo-2-iodobenzaldehyde
this
reaction,
which
pivotal
halogen
bonding
interaction
plays
crucial
role
process.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(7), P. 4958 - 4967
Published: March 18, 2024
Axially
chiral
diarylamine
atropisomers
represent
a
distinct
category
characterized
by
two
contiguous
C–N
axes,
which
exhibit
significantly
lower
racemization
barrier
due
to
the
concerted
rotation
of
both
axes.
In
this
work,
we
introduce
an
effective
method
for
atroposelective
synthesis
axially
diarylamines
through
organocatalyzed
asymmetric
electrophilic
amination
with
azodicarboxylates,
afforded
variety
acyclic
secondary
in
good
yields
high
enantioselectivities.
This
expands
scope
catalytic
beyond
N-aryl
quinoid-type
atropisomers,
enabling
without
constraining
one
axis
intramolecular
hydrogen
bonding.
Both
experimental
and
computational
studies
show
minimal
contribution
bonding
stabilizing
configurations
these
undergo
via
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(12), P. 2403 - 2408
Published: March 19, 2024
The
catalytic
atroposelective
synthesis
of
axially
chiral
heterobiaryls
was
first
developed
through
the
direct
one-step
dynamic
kinetic
condensation
reaction
with
simple
transformation
C═O
bond
to
C═N
bond,
delivering
a
series
novel
heterobiaryl
oxime
ethers.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(16), P. 11089 - 11099
Published: Aug. 1, 2024
In
the
last
several
years,
atropisomers
owing
to
rotational
restriction
around
a
C–N
single
bond
(C–N
axially
chiral
compounds)
have
attracted
significant
attention
in
field
of
synthetic
organic
chemistry.
particular,
highly
enantioselective
synthesis
various
compounds
and
their
application
asymmetric
reactions
been
reported
by
many
groups.
On
other
hand,
studies
on
structural
chemistry
scant
comparison
with
studies.
For
over
25
our
group
has
explored
application.
course
these
studies,
we
found
notable
properties
relation
rotation
an
association
enantiomers
(the
relationship
between
stability
structure
or
electronic
effect,
chirality-dependent
halogen
bond,
self-disproportionation
enantiomers).
Furthermore,
basis
properties,
development
acid-mediated
molecular
rotors
isotopic
possessing
high
stereochemical
purity
were
achieved.
Through
this
Perspective,
I
wish
make
community
aware
that
are
attractive
molecules
from
viewpoints
both
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:
2024,
Volume and Issue:
26(3), P. 681 - 686
Published: Jan. 17, 2024
This
study
presents
the
atroposelective
alkylation
of
2-arylindoles
catalyzed
by
a
substituted
cinchonium
salt
as
phase-transfer
catalyst.
Under
optimized
reaction
conditions,
various
substrates
are
employed
to
yield
products
with
high
enantioselectivity.
The
presence
an
ortho-nitro
group
at
aromatic
ring
is
essential
for
atroposelectivity,
because
it
facilitates
favorable
interactions
between
catalyst
and
substrate.
origin
enantioselectivity
reveals
π–π
both
enantiomers
unfavorable
steric
strains
undesired
enantiomers.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(17), P. 12559 - 12575
Published: Aug. 27, 2024
The
catalytic
atroposelective
synthesis
of
N–N
axially
chiral
indolylamides
was
established
via
dynamic
kinetic
resolution,
which
makes
use
Lewis
base-catalyzed
asymmetric
acylation
N-acylaminoindoles
as
a
new
type
platform
molecule
with
anhydrides.
By
this
strategy,
series
were
synthesized
in
overall
good
yields
(up
to
98%)
excellent
enantioselectivities
99%
ee).
Moreover,
some
these
display
extent
anticancer
activity,
demonstrates
their
potential
application
medicinal
chemistry.
Therefore,
work
has
not
only
provided
strategy
for
the
monoaryl
indoles
but
also
offered
member
configurational
stability
and
promising
application,
thereby
solving
challenges
indoles.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(29), P. 5481 - 5485
Published: July 20, 2023
An
organocatalytic
atroposelective
strategy
for
the
construction
of
axially
chiral
compounds
containing
benzimidazole
and
quinoline
rings
is
described.
The
enantioselective
heteroannulation
reaction
2-alkynylbenzimidazoles
with
ortho-aminophenylketones
proceeded
smoothly
in
presence
phosphoric
acid
to
provide
heterobiaryls
good
yields
enantioselectivities.
This
first
example
combination
at
2-
3-positions,
respectively,
into
by
this
new
strategy.
