Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 17, 2024
Abstract
Transition‐metal
catalyzed
asymmetric
allylic
substitution
with
alkyl
and
heteroaryl
carbon
nucleophiles
has
been
well‐established.
However,
the
arylation
of
acyclic
internal
alkenes
aryl
remains
challenging
underdeveloped.
Herein
we
report
a
stereospecific
3‐aza‐Cope
rearrangement
interrupted
substitution‐isomerization
(
Int‐AASI
)
that
enables
arylation.
By
means
this
stepwise
strategy,
both
enantioenriched
products
axially
chiral
could
be
readily
obtained
in
high
enantioselectivities.
Experimental
studies
support
mechanism
involving
cascade
amination,
alkene
isomerization.
Density
functional
theory
detailed
reasons
achieving
chemoselectivity,
regioselectivity,
stereoselectivity
stereospecificity,
respectively.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: April 16, 2024
Abstract
The
past
century
has
witnessed
a
large
number
of
reports
on
the
Z
/
E
isomerization
alkenes.
However,
vast
majority
them
are
still
limited
to
di-
and
tri-substituted
stereospecific
tetrasubstituted
alkenes
remains
be
an
underdeveloped
area,
thus
lacking
in
stereodivergent
synthesis
axially
chiral
Herein
we
report
atroposelective
alkene
analogues
by
asymmetric
allylic
substitution-isomerization,
followed
their
via
triplet
energy
transfer
photocatalysis.
In
this
regard,
N
-vinylquinolinones
is
achieved
efficiently.
Mechanistic
studies
indicate
that
benzylic
radical
generation
distribution
two
key
factors
for
preserving
enantioselectivities
compounds.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 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.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(24), P. 16567 - 16580
Published: June 7, 2024
Axially
chiral
biaryls
featuring
a
C–N
axis
are
important
functional
molecules
in
diverse
fields.
The
asymmetric
Buchwald–Hartwig
reaction
represents
powerful
strategy
for
these
targets.
Previous
studies,
however,
have
been
predominantly
restricted
to
intramolecular
atroposelective
coupling,
likely
due
the
steric
and
entropic
effects
reductive
elimination
of
Pd(II)
species
with
sterically
congested
aryl
nitrogen
groups.
We
now
report
two
intermolecular
coupling
systems
bulky
NH
lactams
halohydrocarbons
enabled
by
rerouting
mechanism
one
that
accommodates
challenging
substrates.
Both
exhibited
group
tolerance,
excellent
enantioselectivity,
high
Z
selectivity
(if
applicable),
affording
atropisomeric
biaryl
olefins
through
de
novo
construction
axis.
Experimental
computational
studies
were
performed
elucidate
mechanism,
switch
pathways
is
traced
effect
(ortho
substituent)
halide
substrate.
A
2,6-disubstituted
reorients
proximal
lactamide
ligand
its
unusual
O-ligation
mode.
With
amide
oxygen
participation,
this
intermediate
undergoes
an
accessible
barrier
five-membered
ring
transition
state,
pathway
as
well
induction
mode
has
much
underexplored
catalysis.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 24, 2024
Visible
light-driven
photocatalytic
deracemization
is
highly
esteemed
as
an
ideal
tool
for
organic
synthesis
due
to
its
exceptional
atom
economy
and
synthetic
efficiency.
Consequently,
successful
instances
of
allenes
have
been
established,
where
the
activated
energy
photosensitizer
should
surpass
that
substrates,
representing
intrinsic
requirement.
Accordingly,
this
method
not
applicable
axially
chiral
molecules
with
significantly
high
triplet
energies.
In
study,
we
present
a
photoredox
catalytic
approach
enables
efficient
valuable
yet
challenging-to-access
2-azaarene-functionalized
quinazolinones.
The
substrate
scope
extensive,
allowing
both
3-axis
unmet
1-axis
assembly
through
facile
oxidation
diverse
central
2,3-dihydroquinazolin-4(1H)-ones
can
be
easily
prepared
achieve
enantiomer
enrichment
via
deracemization.
Mechanistic
studies
reveal
importance
selection
in
attaining
excellent
chemoselectivity
highlight
indispensability
Brønsted
acid
enabling
enantioselective
protonation
accomplish
Catalysts,
Journal Year:
2025,
Volume and Issue:
15(5), P. 426 - 426
Published: April 27, 2025
Quinazolinones,
a
class
of
nitrogen-containing
heterocyclic
compounds,
occupy
crucial
position
in
medicinal
chemistry
and
materials
science
due
to
their
significant
application
potential.
In
recent
years,
the
catalytic
asymmetric
synthesis
axially
chiral
quinazolinones
has
emerged
as
prominent
research
area,
driven
by
prospective
applications
development
bioactive
molecules,
design
ligands,
fabrication
functional
materials.
This
review
comprehensively
summarizes
advancements
quinazolinones,
with
particular
focus
on
construction
strategies
for
three
major
structural
types:
C–N
axis,
N–N
C–C
axis.
Key
synthetic
methodologies,
including
atroposelective
halogenation,
kinetic
resolution,
condensation–oxidation,
photoredox
deracemization,
are
discussed
detail.
addition,
provides
an
in-depth
analysis
various
systems,
such
peptide
catalysis,
enzymatic
metal
phosphoric
acid
others.
Despite
substantial
progress
made
thus
far,
several
challenges
remain,
expansion
substrate
scope,
enhanced
control
over
stereoselectivity,
further
exploration
practical
applications,
drug
discovery
catalysis.
These
insights
expected
guide
future
towards
novel
strategies,
diversification
variants,
comprehensive
understanding
biological
activities
functions.
Ultimately,
this
will
foster
continued
growth
evolution
rapidly
advancing
field.
Synthesis,
Journal Year:
2023,
Volume and Issue:
56(12), P. 1862 - 1872
Published: Dec. 14, 2023
Abstract
The
construction
of
axially
chiral
alkene
frameworks
is
currently
one
hottest
topics
in
the
field
organic
synthetic
chemistry.
Compared
to
traditional
molecules,
such
as
biaryls,
heterobiaryls,
and
anilides,
synthesis
alkenes
far
more
challenging,
especially
for
acyclic
tetrasubstituted
analogues.
In
this
review,
we
summarized
development
strategies
analogues,
including
asymmetric
difunctionalization,
C–H
functionalization,
cross-coupling,
(dynamic)
kinetic
resolution,
allylic
substitution-isomerization.
1
Introduction
2
Synthesis
Cyclic
Tetrasubstituted
Axially
Chiral
Alkenes
3
Acyclic
4
Summary
Outlook
Chinese Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
44(2), P. 349 - 349
Published: Jan. 1, 2024
Enantioenriched
C-N
axial
chiral
compounds
are
ubiquitous
in
many
important
field,
such
as
natural
products,
drugs
and
ligands.Therefore,
efficient
construction
of
axis
chirality
through
asymmetric
catalytic
synthesis
has
attracted
more
attention
research
interest.In
this
review,
the
recent
progress
been
discussed,
mainly
from
three
aspects:
desymmetrization
prochiral
molecules
or
kinetic
resolution
racemates,
atroposelective
functionalization
axis,
coupling
reaction.The
topic
focuses
on
evolution
system
key
factors
control.The
existing
problems
future
development
direction
field
also
discussed.This
paper
is
a
timely
systematic
review
will
stimulate
extensive
interest.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(43)
Published: July 24, 2024
Abstract
Visible
light‐driven
photocatalytic
deracemization
is
highly
esteemed
as
an
ideal
tool
for
organic
synthesis
due
to
its
exceptional
atom
economy
and
synthetic
efficiency.
Consequently,
successful
instances
of
allenes
have
been
established,
where
the
activated
energy
photosensitizer
should
surpass
that
substrates,
representing
intrinsic
requirement.
Accordingly,
this
method
not
applicable
axially
chiral
molecules
with
significantly
high
triplet
energies.
In
study,
we
present
a
photoredox
catalytic
approach
enables
efficient
valuable
yet
challenging‐to‐access
2‐azaarene‐functionalized
quinazolinones.
The
substrate
scope
extensive,
allowing
both
3‐axis
unmet
1‐axis
assembly
through
facile
oxidation
diverse
central
2,3‐dihydroquinazolin‐4(1
H
)‐ones
can
be
easily
prepared
achieve
enantiomer
enrichment
via
deracemization.
Mechanistic
studies
reveal
importance
selection
in
attaining
excellent
chemoselectivity
highlight
indispensability
Brønsted
acid
enabling
enantioselective
protonation
accomplish
