Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(31), P. 6725 - 6729
Published: July 29, 2024
A
two-step
protocol
including
an
enantioselective
organocatalyzed
synthesis
of
pyrroloquinolines
followed
by
oxidation
reaction
allowed
the
formation
axially
chiral
2-aryl-pyrroloquinolones.
Thorough
optimization
experimental
conditions
for
second
step
oxygenation
to
take
place
and
ensured,
in
most
cases,
a
central-to-axial
chirality
conversion
with
complete
retention
enantiomeric
excess.
Accounts of Chemical Research,
Journal Year:
2023,
Volume and Issue:
56(18), P. 2537 - 2554
Published: Sept. 11, 2023
ConspectusAtropisomers
bearing
a
rotation-restricted
axis
are
common
structural
units
in
natural
products,
chiral
ligands,
and
drugs;
thus,
the
prevalence
of
asymmetric
synthesis
has
increased
recent
decades.
Research
into
atropisomers
featuring
an
N-containing
(N-X
atropisomers)
remains
its
infancy
compared
with
well-developed
C-C
atropisomer
analogue.
Notably,
N-X
could
offer
divergent
scaffolds,
which
extremely
important
bioactive
molecules.
The
is
recognized
as
both
appealing
challenging.
Recently,
we
devoted
our
efforts
to
catalytic
atropisomers,
benzimidazole-aryl
N-C
indole-aryl
hydrogen-bond-assisted
pyrrole-pyrrole
N-N
pyrrole-indole
indole-indole
atropisomers.
To
obtain
Buchwald-Hartwig
reaction
amidines
or
enamines
was
employed.
Using
Pd(OAc)2/(S)-BINAP
Pd(OAc)2/(S)-Xyl-BINAP
catalyst
system,
were
readily
obtained.
address
issue
reduced
stability
diarylamine
axis,
six-membered
intramolecular
N-H-O
hydrogen
bond
introduced
scaffold.
A
tandem
N-arylation/oxidation
process
used
for
phosphoric
acid
(CPA)-catalyzed
N-aryl
quinone
For
copper-mediated
Friedel-Crafts
alkylation/arylation
developed.
desymmetrization
completed
successfully
via
Cu(OTf)2/chiral
bisoxazoline
(CuOTf)·Tol/bis(phosphine)
dioxide
thereby
achieving
first
N/N
bipyrrole
Asymmetric
amination
utilized
provide
bisindole
excellent
stereogenic
control.
This
scaffold
using
de
novo
indole
construction
strategy.
heterobiaryl
substantially
facilitated
palladium-catalyzed
transient
directing
group
(TDG)-mediated
C-H
functionalization.
Atropisomeric
alkenylation,
allylation,
alkynylation
accomplished
Pd(OAc)2/l-tert-leucine
system.
Herein,
summarize
work
on
palladium-,
copper-,
CPA-catalyzed
syntheses
Furthermore,
application
molecule
analogues
axially
ligands
demonstrated.
Subsequently,
briefly
discussed
terms
single
crystals
obtained
rotational
barriers.
Finally,
outlook
provided.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(8), P. 5493 - 5501
Published: Feb. 13, 2024
Larock
indole
synthesis
is
one
of
the
most
straightforward
and
efficient
methods
for
indoles;
however,
there
has
been
no
asymmetric
version
yet
construction
indole-based
axially
chiral
N-arylindoles
since
its
initial
report
in
1991.
Herein
we
first
example
an
by
employing
a
sulfinamide
phosphine
(SadPhos)
ligand
(Ming-Phos)
with
palladium.
It
allows
rapid
wide
range
N-arylindole
compounds
good
yields
up
to
98:2
er.
The
application
this
unique
scaffold
as
organocatalyst
promising.
Furthermore,
kinetic
study
revealed
that
alkyne
migratory
insertion
rate-determining
step,
which
proven
density
functional
theory
(DFT)
calculations.
Additionally,
DFT
studies
also
suggest
N–C
dihedral
difference
caused
steric
hindrance
contributes
enantioselectivity
control.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
53(2), P. 883 - 971
Published: Dec. 18, 2023
This
review
aims
to
collect
advancements
in
enantioselective
palladium-catalyzed
cyclization
reactions
over
the
past
eleven
years,
and
it
is
organized
into
thirteen
sections
depending
on
different
types
of
transformations
involved.
Precision Chemistry,
Journal Year:
2024,
Volume and Issue:
2(5), P. 208 - 220
Published: April 23, 2024
The
catalytic
asymmetric
diastereodivergent
synthesis
of
axially
chiral
2-alkenylindoles
was
established
via
phosphoric
acid-catalyzed
addition
reactions
C3-unsubstituted
with
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(19), P. 9560 - 9581
Published: Jan. 1, 2024
Chiral
amine
scaffolds
are
among
the
most
important
building
blocks
in
natural
products,
drug
molecules,
and
functional
materials,
which
have
prompted
chemists
to
focus
more
on
their
synthesis.
Among
accomplishments
chiral
synthesis,
transition-metal-catalyzed
enantioselective
C-N
cross-coupling
is
considered
one
of
efficient
protocols.
This
approach
combines
traditional
C(sp
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(42), P. 29214 - 29223
Published: Oct. 9, 2024
Macrocycles
incorporating
conformationally
defined
indoles
are
widely
found
in
bioactive
natural
products.
However,
the
catalytic
enantioselective
synthesis
of
planar-chiral
via
indolization
involving
macrocyclization
remains
elusive.
Herein,
we
present
first
rhodium(III)-catalyzed
atroposelective
macrocyclization,
which
involves
C-H
activation
aniline,
and
a
subsequent
oxidation
[3
+
2]
annulation
reaction
with
an
intramolecular
alkyne.
This
protocol
achieves
construction
indoles,
planar
chirality
control
single
step.
Importantly,
this
strategy
produces
macrocyclic
atropisomers
bearing
full-carbon
ansa
chains,
represent
challenging
targets
organic
synthesis.
Thermodynamic
experiments
revealed
that
rotational
barrier
chain-linked
atropisomer
was
lower
than
oxa-ansa
chain.
The
mechanism
elucidated
by
computational
studies,
alkyne
insertion
steps
collectively
determined
enantioselectivity.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 13, 2025
C–N
axially
chiral
compounds
represent
an
important
class
of
atropisomers
that
are
prevalent
in
bioactive
and
material
molecules.
Despite
recent
advances
synthetic
methodologies,
the
asymmetric
construction
featuring
multiple
axes
has
been
rarely
explored,
significantly
limiting
their
further
applications.
Herein,
we
report
a
novel
atroposelective
synthesis
diaxially
pyridoindolones
both
six–five
six–six
through
cobalt-catalyzed
C–H
annulation.
This
approach
demonstrates
exceptional
efficiency,
yielding
diverse
array
with
excellent
yields
atroposelectivities
(60
examples,
up
to
>99%
yield,
ee,
>20:1
dr).
Mechanistic
studies
revealed
stereochemistry
were
generated
fixed
simultaneously
during
cyclometalation
step,
along
unexpected
amplification
effect.
The
practicality
this
protocol
is
underscored
by
successful
gram-scale
syntheses
various
transformations,
including
formation
phosphine
ligand.
Notably,
photoluminescence
quantum
(ΦF
0.99)
positive
solvatochromism
observed,
coupled
significant
chiroptical
properties,
underscoring
potential
applications
these
organic
fluorescent
materials.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(21), P. 2788 - 2792
Published: July 3, 2023
Comprehensive
Summary
Axially
chiral
N
‐arylindoles
bearing
a
stereogenic
C—N
axis
are
unique
important
scaffolds
in
natural
products,
advance
materials,
pharmaceuticals
and
privileged
ligands
or
catalysts.
Herein,
we
report
the
direct
synthesis
of
axially
through
Pd‐catalyzed
free
amine‐directed
atroposelective
C—H
olefination
enabled
by
spiro
phosphoric
acid
(SPA)
ligand.
A
wide
range
enantioenriched
‐aromatic
amine
indoles
were
obtained
high
yields
with
good
enantioselectivities
(35
examples,
up
to
91%
yield
96%
ee).
The
products
group
offer
an
effective
functional
handle
for
down‐stream
diversity‐oriented
synthesis.
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.