Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(24)
Published: March 25, 2022
Ladderane
phospholipids,
with
their
unusual
ladder-like
arrangement
of
concatenated
cyclobutane
rings,
represent
an
architecturally
unique
class
natural
products.
However,
despite
fascinating
structure
and
other
necessary
impetus,
only
a
few
synthetic
studies
these
molecules
have
been
reported
so
far.
We
now
devised
concise
total
synthesis
[3]-ladderanol,
component
ladderane
using
organocatalytic
enantioselective
desymmetrizing
formal
C(sp2
)-H
alkylation.
Our
strategy
rests
on
the
late-stage
introduction
chirality,
thus
allowing
facile
access
to
both
enantiomers
[3]-ladderanol
as
well
analogue.
This
is
first
time
desymmetrization
applied
[3]-ladderanol.
The
scope
this
alkylation
meso-cyclobutane-fused
cyclohexenediones
also
presented.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(9), P. 4918 - 4937
Published: April 12, 2022
Although
Suzuki–Miyaura
cross-coupling
is
one
of
the
most
convenient
and
well-developed
reactions,
its
applications
to
asymmetric
version
deliver
highly
functionalized
atropisomers
or
nonracemic
coupling
products
have
been
less
explored.
Besides
some
excellent
work
reported
intermittently,
reaction
remains
a
significant
challenge,
particularly
for
preparing
heterocyclic
atropisomers.
A
concise
but
critical
knowledge
on
this
topic
may
further
inspire
researchers
across
various
subdisciplines
develop
innovative
practical
solutions
tackle
problem.
Therefore,
Review
aims
summarize
pioneering
cross-couplings
cover
implementations
via
homogeneous
heterogeneous
catalysis
during
recent
years.
Most
notably,
use
transition
metals
other
than
palladium
also
described.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(33), P. 15026 - 15032
Published: Aug. 15, 2022
Axial
chirality
features
prominently
in
molecules
of
biological
interest
as
well
chiral
catalyst
designs,
and
atropisomeric
2,2′-biphenols
are
particularly
prevalent.
Atroposelective
metal-catalyzed
cross-coupling
is
an
attractive
modular
approach
to
access
enantioenriched
biphenols,
yet
existing
protocols
cannot
achieve
this
directly.
We
address
challenge
through
the
use
enantiopure,
sulfonated
SPhos
(sSPhos),
ligand
that
has
until
now
been
used
only
racemic
form
derives
its
from
axis
introduced
sulfonation.
believe
noncovalent
interactions
involving
sulfonate
group
responsible
for
high
levels
asymmetric
induction
we
obtain
2,2′-biphenol
products
Suzuki–Miyaura
coupling,
have
developed
a
highly
practical
resolution
sSPhos
via
diastereomeric
salt
recrystallization.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(9), P. 6283 - 6293
Published: Feb. 21, 2024
We
herein
introduce
biarylhemiboronic
esters
as
a
new
type
of
bridged
biaryl
reagent
for
asymmetric
synthesis
axially
chiral
structures,
and
the
palladium-catalyzed
Suzuki-Miyaura
cross-coupling
is
developed.
This
dynamic
kinetic
atroposelective
coupling
reaction
exhibits
high
enantioselectivity,
good
functional
group
tolerance,
broad
substrate
scope.
The
synthetic
application
current
method
was
demonstrated
by
transformations
product
programmed
polyarene.
Preliminary
mechanistic
studies
suggested
that
proceeded
via
an
enantio-determining
transmetalation
step.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: March 10, 2025
Pillar[n]arenes
have
broad
applications
in
biological
medicine,
materials
science,
and
supramolecular
gels.
Notably,
enantiopure
pillar[5]arenes
are
valued
for
their
roles
enantioselective
host–guest
recognition,
chiral
sensing,
asymmetric
catalysis,
related
fields.
Current
methods
obtaining
pillar[n]arenes
rely
heavily
on
resolution
agents
or
HPLC
resolution.
However,
the
synthesis
of
these
compounds
via
catalysis
remains
challenging.
In
this
study,
we
develop
an
extended
side-arm
Suzuki–Miyaura
cross-coupling
strategy
to
construct
inherently
with
excellent
yields
high
enantioselectivities
using
a
palladium
catalyst
Sadphos
ligand.
The
reaction
scope
extends
beyond
arylboronic
acids
encompass
2-arylvinylboronic
other
multi-OTf-substituted
substrates,
all
efficiently
producing
desired
products.
Further
exploration
synthetic
applications,
along
photophysical
chiroptical
analyses,
confirm
potential
diverse
across
multiple
disciplines.
Enantiopure
recognition
but
current
Here,
authors
pillar[5]arenes.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(5), P. 2884 - 2900
Published: Jan. 25, 2023
The
involvement
of
planar
carbocation
intermediates
is
generally
considered
undesirable
in
asymmetric
catalysis
due
to
the
difficulty
gaining
facial
control
and
their
intrinsic
stability
issues.
Recently,
suitably
designed
chiral
catalyst(s)
have
enabled
a
guided
approach
nucleophiles
one
prochiral
faces
carbocations
affording
high
enantiocontrol.
Herein,
we
present
vital
mechanistic
insights
from
our
comprehensive
density
functional
theory
(B3LYP-D3)
study
on
Ir-phosphoramidite-catalyzed
reductive
deoxygenation
racemic
tertiary
α-substituted
allenylic
alcohols.
catalytic
transformation
relies
synergistic
action
phosphoramidite-modified
Ir
catalyst
Bi(OTf)3,
first
leading
formation
an
Ir-π-allenyl
intermediate
through
turn-over-determining
SN1
ionization,
followed
by
face-selective
hydride
transfer
Hantzsch
ester
analogue
yield
enantioenriched
product.
Bi(OTf)3
was
found
promote
significant
number
ionic
interactions
as
well
noncovalent
(NCIs)
with
substrates
(allenylic
alcohol
ester),
thus
providing
access
lower
energy
route
compared
pathways
devoid
Bi(OTf)3.
In
nucleophilic
addition,
induction
depend
efficacy
such
key
NCIs.
curious
case
reversal
enantioselectivity,
when
α-substituent
allenyl
changed
methyl
cyclopropyl,
identified
originate
change
mechanism
enantioconvergent
pathway
(α-methyl)
dynamic
kinetic
(α-cyclopropyl).
These
molecular
could
lead
newer
strategies
tame
enantioselective
reactions
using
suitable
combinations
catalysts
additives.
