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
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.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Aug. 29, 2023
The
N-N
atropisomer,
as
an
important
and
intriguing
chiral
system,
was
widely
present
in
natural
products,
pharmaceutical
lead
compounds,
advanced
material
skeletons.
anisotropic
structural
characteristics
caused
by
its
special
axial
rotation
have
always
been
one
of
the
challenges
that
chemists
strive
to
overcome.
Herein,
we
report
efficient
method
for
enantioselective
synthesis
axially
frameworks
via
a
cobalt-catalyzed
atroposelective
C-H
activation/annulation
process.
reaction
proceeds
under
mild
conditions
using
Co(OAc)2·4H2O
catalyst
with
salicyl-oxazoline
(Salox)
ligand
O2
oxidant,
affording
variety
products
high
yields
enantioselectivities.
This
protocol
provides
approach
facile
construction
atropisomers
further
expands
range
derivatives.
Additionally,
electrocatalysis,
desired
were
also
successfully
achieved
good
excellent
efficiencies
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.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Jan. 7, 2025
3-Amino
boron
dipyrromethenes
(BODIPYs)
are
a
versatile
class
of
fluorophores
widely
utilized
in
live
cell
imaging,
photodynamic
therapy,
and
fluorescent
materials
science.
Despite
the
growing
demand
for
optically
active
BODIPYs,
synthesis
chiral
3-amino-BODIPYs,
particularly
catalytic
asymmetric
version,
remains
challenge.
Herein,
we
report
boron-stereogenic
3-amino-BODIPYs
via
palladium-catalyzed
desymmetric
C–N
cross-coupling
prochiral
3,5-dihalogen-BODIPYs.
This
approach
features
broad
substrate
scope,
excellent
functional
group
tolerance,
high
efficiency,
remarkable
enantioselectivities,
under
mild
reaction
conditions.
Further
stereospecific
formation
3,5-diamino-BODIPYs,
along
with
an
investigation
into
photophysical
properties
resulting
optical
BODIPYs
also
explored.
protocol
not
only
enriches
chemical
space
chiroptical
BODIPY
dyes
but
contributes
to
realm
chemistry.
(BODIPYs),
which
useful
science,
authors
first
cross-couplings.
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.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(27), P. 4036 - 4039
Published: Jan. 1, 2023
The
synthesis
of
N-naphthyl
pyrazoles
has
been
realized
by
the
direct
three-component
reactions
enaminones,
aryl
hydrazine
hydrochlorides
and
internal
alkynes
via
Rh(III)
catalysis.
synthetic
employing
simple
substrates
lead
to
simultaneous
construction
dual
cyclic
moieties,
including
a
pyrazole
ring
phenyl
ring,
sequential
formation
two
C-N
three
C-C
bonds.
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
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(11), P. 7680 - 7690
Published: May 23, 2023
The
transition-metal-catalyzed
cross-coupling
of
enamines
is
an
attractive
method
for
producing
compounds
with
N–C
chiral
axis;
however,
it
faces
considerable
challenges
that
remain
unresolved.
Herein,
a
palladium-catalyzed
amination
was
developed
to
construct
structurally
diverse
five–six
biaryl
and
six–six
nonbiaryl
atropisomers.
reaction
mechanism
explained
using
density
functional
theory
calculations,
which
showed
the
involved
Curtin–Hammett
control.
rotation
occurred
along
coordinate
until
enantio-determining
three-centered
reductive
elimination
transition
structure
established
stereochemistry.
highly
because
its
broad
substrate
scope,
high
stereoselectivity,
simple
catalytic
system,
good
group
tolerance,
dynamic
kinetic
resolution.