Beilstein Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
20, P. 3221 - 3255
Published: Dec. 10, 2024
Asymmetric
cycloaddition
is
a
straightforward
strategy
which
enables
the
synthesis
of
structurally
distinct
cyclic
derivatives
are
difficult
to
access
by
other
methodologies,
using
an
efficient
and
atom-economical
path
from
simple
precursors.
In
recent
years
several
asymmetric
catalytic
cyclization
strategies
have
been
accomplished
for
construction
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(21)
Published: March 21, 2023
The
catalytic
asymmetric
construction
of
N-N
atropisomeric
biaryls
remains
a
formidable
challenge.
Studies
them
lag
far
behind
studies
the
more
classical
carbon-carbon
biaryl
atropisomers,
hampering
meaningful
development.
Herein,
first
palladium-catalyzed
enantioselective
C-H
activation
pyrroles
for
synthesis
atropisomers
is
presented.
Structurally
diverse
indole-pyrrole
possessing
chiral
axis
were
produced
with
good
yields
and
high
enantioselectivities
by
alkenylation,
alkynylation,
allylation,
or
arylation
reactions.
Furthermore,
kinetic
resolution
trisubstituted
heterobiaryls
sterically
demanding
substituents
was
also
achieved.
Importantly,
this
versatile
functionalization
strategy
enables
iterative
exquisite
selectivity,
expediting
formation
valuable,
complex,
atropisomers.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(4), P. 2565 - 2575
Published: Feb. 6, 2023
We
present
herein
an
unprecedented
stereoselective
synthesis
of
triaryl-2-pyrones
with
monoaxial
or
contiguous
diaxes
from
readily
available
starting
materials.
This
N-heterocyclic
carbene
catalysis
method
adopts
atroposelective
annulation
2-aryketones
ynals
under
oxidative
conditions.
The
includes
the
construction
one
two
axes
in
a
single
operation,
achieves
step
economy,
and
affords
axially
chiral
moderate
to
good
yields,
high
excellent
enantioselectivities.
DFT
calculations
relative
energies
stereoisomers
rotational
barriers
were
performed.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(23)
Published: March 30, 2023
Axially
chiral
biaryls
widely
exist
in
natural
products
and
pharmaceuticals
are
used
as
ligands
catalysts
asymmetric
synthesis.
Compared
to
the
well-established
axially
6-membered
biaryl
skeletons,
examples
of
5-membered
have
been
quite
scarce,
mono-substituted
3-arylpyrrole
atropisomers
not
reported.
Here,
we
disclose
a
copper-catalyzed
atroposelective
diyne
cyclization
for
construction
range
arylpyrrole
good
excellent
yields
with
generally
enantioselectivities
via
oxidation
X-H
insertion
vinyl
cations.
Importantly,
this
protocol
only
represents
first
synthesis
atropisomers,
but
also
constitutes
example
atropisomer
Theoretical
calculations
further
support
mechanism
cation-involved
elucidate
origin
enantioselectivity.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Aug. 9, 2023
The
C-N
axially
chiral
N-arylpyrrole
motifs
are
privileged
scaffolds
in
numerous
biologically
active
molecules
and
natural
products,
as
well
ligands/catalysts.
Asymmetric
synthesis
of
N-arylpyrroles,
however,
is
still
challenging,
the
simultaneous
creation
contiguous
axial
central
chirality
remains
unknown.
Herein,
a
diastereo-
atroposelective
N-arylpyrroles
enabled
by
light-induced
phosphoric
acid
catalysis
has
been
developed.
key
transformation
one-pot,
three-component
oxo-diarylation
reaction,
which
simultaneously
creates
quaternary
stereogenic
center.
A
broad
range
unactivated
alkynes
were
readily
employed
reaction
partner
this
transformation,
products
obtained
good
yields,
with
excellent
enantioselectivities
very
diastereoselectivities.
Notably,
skeletons
represent
interesting
structural
that
could
be
used
ligands
catalysts
asymmetric
catalysis.
Beilstein Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
21, P. 55 - 121
Published: Jan. 9, 2025
Axial
chirality
is
present
in
a
variety
of
naturally
occurring
compounds,
and
becoming
increasingly
relevant
also
medicine.
Many
axially
chiral
compounds
are
important
as
catalysts
asymmetric
catalysis
or
have
chiroptical
properties.
This
review
overviews
recent
progress
the
synthesis
via
organocatalysis.
Atroposelective
organocatalytic
reactions
discussed
according
to
dominant
catalyst
activation
mode.
For
covalent
organocatalysis,
typical
enamine
iminium
modes
presented,
followed
by
N
-heterocyclic
carbene-catalyzed
reactions.
The
bulk
devoted
non-covalent
activation,
where
Brønsted
acids
feature
most
prolific
catalytic
structure.
last
part
article
discusses
hydrogen-bond-donating
other
motifs
such
phase-transfer
catalysts.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(27)
Published: March 6, 2023
Atropisomeric
heterobiaryls
play
a
vital
role
in
natural
products,
chiral
ligands,
organocatalysts,
and
other
research
fields,
which
have
aroused
great
interest
from
chemists
recent
years.
Until
now,
growing
number
of
optically
active
based
on
indole,
quinoline,
isoquinoline,
pyridine,
pyrrole,
azole,
benzofuran
skeletons
been
successfully
synthesized
through
metal
or
organic
catalytic
cross-coupling,
functionalization
prochiral
racemic
heterobiaryls,
ring
formation.
Among
different
strategies
for
the
atroposelective
synthesis
strategy
formation
has
become
tool
toward
this
goal.
In
review,
we
summarize
enantioselective
axially
approaches,
such
as
cycloaddition,
cyclization,
chirality
conversion.
Meanwhile,
reaction
mechanism
corresponding
applications
are
also
discussed.
ACS Central Science,
Journal Year:
2023,
Volume and Issue:
9(9), P. 1758 - 1767
Published: Aug. 15, 2023
Heterocyclic
scaffolds
are
commonly
found
in
numerous
biologically
active
molecules,
therapeutic
agents,
and
agrochemicals.
To
probe
chemical
space
around
heterocycles,
many
powerful
molecular
editing
strategies
have
been
devised.
Versatile
C-H
functionalization
allow
for
peripheral
modifications
of
heterocyclic
motifs,
often
being
specific
taking
place
at
multiple
sites.
The
past
few
years
seen
the
quick
emergence
exciting
"single-atom
skeletal
editing"
strategies,
through
one-atom
deletion
or
addition,
enabling
ring
contraction/expansion
structural
diversification,
as
well
scaffold
hopping.
construction
heterocycles
via
deconstruction
simple
is
unknown.
Herein,
we
disclose
a
new
method
which
name
recasting
strategy.
Specifically,
by
tapping
on
1,3-dipolar
property
azoalkenes,
recast
pyrroles
to
fully
substituted
pyrroles,
phosphoric
acid-promoted
one-pot
reaction
consisting
dearomative
rearomative
reconstruction
steps.
allows
easy
access
synthetically
challenging
tetra-substituted
otherwise
difficult
synthesize.
Furthermore,
construct
N-N
axial
chirality
our
pyrrole
products,
accomplish
facile
synthesis
anticancer
drug,
Sutent.
potential
application
this
other
has
also
demonstrated.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Aug. 25, 2023
Abstract
The
catalytic
asymmetric
dearomatization
(CADA)
reaction
has
proved
to
be
a
powerful
protocol
for
rapid
assembly
of
valuable
three-dimensional
cyclic
compounds
from
readily
available
planar
aromatics.
In
contrast
the
well-studied
indoles
and
naphthols,
phenols
have
been
considered
challenging
substrates
intermolecular
CADA
reactions
due
combination
strong
aromaticity
potential
regioselectivity
issue
over
multiple
nucleophilic
sites
(O,
C2
as
well
C4).
Reported
herein
are
chiral
phosphoric
acid-catalyzed
divergent
common
with
azoalkenes,
which
deliver
tetrahydroindolone
cyclohexadienone
products
bearing
an
all-carbon
quaternary
stereogenic
center
in
good
yields
excellent
ee
values.
Notably,
simply
adjusting
temperature
leads
chemo-divergent
(3
+
2)
alkylation
reactions.
Moreover,
stereo-divergent
synthesis
four
possible
stereoisomers
kind
achieved
via
changing
sequence
catalyst
enantiomers.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Aug. 10, 2024
The
construction
of
atropisomers
with
1,2-diaxes,
while
maintaining
high
enantiocontrol,
presents
a
significant
challenge
due
to
the
dynamic
nature
steric
hindrance
at
ortho-aryl
substituents.
Although
various
catalytic
asymmetric
methods
have
been
developed
for
accessing
axially
chiral
arylpyrroles,
synthesis
arylpyrroles
1,2-diaxes
in
manner
has
remained
rare.
Herein,
authors
report
diverse
and
C-C
C-N
axes
through
copper-catalysed
asymmetirc
[4
+
1]
annulation
yne-allylic
esters
arylamines
via
remote
stereocontrol
strategy.
This
approach
provides
facile
access
broad
range
heterobiaryl
(67
examples)
excellent
enantioselectivities,
each
bearing
one
or
two
C-C/C-N
axes,
demonstrating
its
versatility
efficiency.
utility
this
methodology
is
further
highlighted
by
transformation
product
into
phosphine
ligand,
thioureas
use
catalysis.