Angewandte Chemie,
Год журнала:
2024,
Номер
136(42)
Опубликована: Авг. 6, 2024
Abstract
Planar‐chiral
skeletons
widely
exist
in
natural
products,
bioactive
compounds,
and
other
functional
molecules.
Although
significant
progress
has
been
made
the
field
of
asymmetric
synthesis
centrally
or
axially
chiral
molecules
over
past
years,
enantioselective
constructing
planar
chirality
is
still
a
big
obstacle
numerous
efforts
have
this
field.
Previous
works
mainly
focused
on
assembly
planar‐chiral
[2,2]‐paracyclophanes
metallocenes.
This
Minireview
describes
recent
advancements
catalytic
macrocycles,
including
ansa
chain
construction,
plane
formation
transformation
strategies.
It
anticipated
that
will
sever
as
source
inspiration
for
developing
new
unconventional
procedures
access
to
skeletons.
Organic Letters,
Год журнала:
2024,
Номер
26(5), С. 1040 - 1045
Опубликована: Янв. 31, 2024
An
N-heterocyclic
carbene
(NHC)-catalyzed
atroposelective
macrolactonization
has
been
disclosed.
This
approach
affords
planar-chiral
macrocycles
in
high
yields
with
excellent
enantioselectivities
over
a
broad
substrate
scope.
Controlled
experiments
suggest
that
the
enantioselectivity
might
arise
from
cation–n
interaction
between
acyl
azolium
and
electron-rich
moiety
substrate.
mechanism
is
supported
by
density
functional
theory
calculations,
which
also
an
important
π–π
stabilizing
transition
state.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(42), С. 29214 - 29223
Опубликована: Окт. 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.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Март 3, 2025
A
highly
enantioselective
electrophilic
selenylation/semipinacol
rearrangement
of
allenols
has
been
developed,
which
is
enabled
by
the
cooperative
catalysis
a
chiral
sulfide
and
an
achiral
sulfonic
acid.
The
designed
synthesized
catalyst
selenylating
reagent
play
crucial
role
in
enhancing
both
enantioselectivity
reactivity.
This
approach
exhibits
excellent
regio-,
chemo-,
enantioselectivity,
providing
access
to
diverse
enantioenriched
cyclopentanones
featuring
arylselenovinyl-substituted
quaternary
carbon
stereocenter.
Furthermore,
these
products
can
be
transformed
into
synthetically
valuable
alkyne,
vinyl
bromide,
aniline
derivatives.
Mechanistic
studies
reveal
that
combination
acid
not
only
facilitates
formation
catalytically
active
species,
but
also
governs
reaction.
Meanwhile,
density
functional
theory
calculations
disclose
four
hydrogen
bond
interactions
π‧‧‧π
interaction
are
responsible
for
observed
enantioselectivity.
Rearrangement
reactions
serve
as
steps
syntheses
biologically
provide
intellectual
conceptual
curiosities
within
broad
field
organic
chemistry.
Here,
authors
report
allenols,
catalysed
Lewis
base.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Ноя. 15, 2024
Inherently
chiral
calixarenes
hold
great
potential
for
applications
in
recognition,
sensing,
and
asymmetric
catalysis
due
to
their
unique
structures.
However,
special
structures
relatively
large
sizes,
the
catalytic
synthesis
of
inherently
is
challenging
with
very
limited
examples
available.
Here,
we
present
an
efficient
method
enantioselective
sulfur-containing
calix[4]arenes
through
desymmetrizing
electrophilic
sulfenylation
calix[4]arenes.
This
reaction
enabled
by
a
1,1'-binaphthyl-2,2'-diamine-derived
sulfide
catalyst
hexafluoroisopropanol.
Various
are
obtained
moderate
excellent
yields
high
enantioselectivities.
Control
experiments
indicate
that
thermodynamically
favored
C-SAr
product
formed
from
kinetically
N-SAr
combination
hexafluoroisopropanol
crucially
important
both
enantioselectivity
reactivity.
Due
authors
report
Chemical Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
Planar-chiral
macrocycles
play
a
pivotal
role
in
host-guest
chemistry
and
drug
discovery.
However,
compared
with
the
synthesis
of
other
types
chiral
compounds,
asymmetric
construction
planar-chiral
still
remains
forbidding
challenge.
Herein,
we
report
sequential
palladium
N-heterocyclic
carbene
catalysis
to
build
macrocycles.
This
protocol
features
broad
scope
good
functional
group
tolerance,
allows
rapid
assembling
excellent
enantioselectivities.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
43(11), С. 1263 - 1270
Опубликована: Март 7, 2025
Comprehensive
Summary
Planar‐chiral
cyclophanes
with
carbon‐centered
chirality
are
important
targets
in
natural
products
and
pharmaceuticals.
However,
synthesizing
such
planar
chiral
two
stereogenic
elements
via
a
one‐step
asymmetric
reaction
remains
formidable
challenge.
Herein,
we
present
an
efficient
kinetic
resolution
method
for
planar‐chiral
[
n
]cyclophanes
chirality.
This
is
achieved
through
the
enantioselective
allylation
of
racemic
aldehyde
catalyzed
by
Bi(OAc)
3
phosphoric
acid.
The
delivers
multiple
high
yields
excellent
enantioselectivities,
showcasing
remarkable
efficiency
(
s
factor
up
to
292).
broad
substrate
scope,
scalability,
potential
derivatization
highlight
value
this
methodology.
DFT
calculations
have
also
been
performed
provide
insights
into
origin
experimentally
observed
diastereo‐
enantioselectivity
reaction.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 6, 2024
Planar-chiral
skeletons
widely
exist
in
natural
products,
bioactive
compounds,
and
other
functional
molecules.
Although
significant
progress
has
been
made
the
field
of
asymmetric
synthesis
centrally
or
axially
chiral
molecules
over
past
years,
enantioselective
constructing
planar
chirality
is
still
a
big
obstacle
numerous
efforts
have
this
field.
Previous
works
mainly
focused
on
assembly
planar-chiral
[2,2]-paracyclophanes
metallocenes.
This
Minireview
describes
recent
advancements
catalytic
macrocycles,
including
ansa
chain
construction,
plane
formation
transformation
strategies.
It
anticipated
that
will
sever
as
source
inspiration
for
developing
new
unconventional
procedures
access
to
skeletons.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(47)
Опубликована: Авг. 28, 2024
Abstract
The
planar
chirality
of
macrocycles
is
a
fascinating
research
topic.
Locking
the
configurational
flip
between
benzene
ring
and
macrocycle
leads
to
chirality,
which
can
significantly
enhance
biological
activity
cyclophanes.
Planar‐chiral
cyclophanes
are
widely
used
in
pharmaceuticals,
chiral
catalysts,
functional
materials.
However,
accessing
planar‐chiral
via
asymmetric
catalysis
has
remained
challenging.
Among
various
strategies,
macrocyclization
provides
powerful
tool
for
This
method
allows
control
when
constructing
greatly
improves
efficiency.
There
three
types
reactions:
transition
metal‐catalyzed,
organocatalyzed,
biocatalyzed.
In
addition,
confinement
strategy
breaks
through
conservative
synthetic
approaches.
review
summarizes
these
achievements,
aiming
highlight
catalytic
synthesis
inspire
interested
researchers.
