Molecules,
Journal Year:
2025,
Volume and Issue:
30(3), P. 603 - 603
Published: Jan. 29, 2025
Enantiopure
turbo
chirality
in
small
organic
molecules,
without
other
chiral
elements,
is
a
fascinating
topic
that
has
garnered
significant
interest
within
the
chemical
and
materials
science
community.
However,
further
research
into
application
of
this
concept
have
been
severely
limited
by
lack
effective
asymmetric
tools.
To
date,
only
few
enantiomers
targets
isolated,
these
were
obtained
through
physical
separation
using
HPLC,
typically
on
milligram
scales.
In
work,
we
report
first
approach
to
enantiopure
absence
elements
such
as
central
axial
chirality.
This
demonstrated
assembling
aromatic
phosphine
oxides,
where
three
propeller-like
groups
are
anchored
P(O)
center
via
axes.
Asymmetric
induction
was
successfully
carried
out
sulfonimine
auxiliary,
with
absolute
configurations
conformations
unambiguously
determined
X-ray
diffraction
analysis.
The
resulting
frameworks
exhibit
propellers
arranged
either
clockwise
(P,P,P)
or
counterclockwise
(M,M,M)
configuration.
arrangements,
bulkier
sides
rings
oriented
toward
oxygen
atom
P=O
bond
rather
than
opposite
direction.
Additionally,
orientational
configuration
controlled
auxiliary
well,
showing
one
Naph
pushed
away
from
group
(-CH2-NHSO2-tBu)
phenyl
ring.
Computational
studies
conducted
relative
energies
for
rotational
barriers
target
along
axis
transition
pathway
between
two
enantiomers,
meeting
our
expectations.
work
expected
impact
fields
chemistry,
biomedicine,
future.
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
28(29)
Published: March 16, 2022
Dynamic
deracemization
processes,
such
as
crystallization-induced
diastereomer
transformations
(CIDTs),
offer
the
opportunity
to
combine
racemization
and
resolution
provide
high
yields
of
enantiomerically
pure
compounds.
To
date,
few
these
processes
have
incorporated
photochemical
racemization.
By
combining
batch
crystallization
with
a
flow
photoreactor
for
efficient
irradiation,
it
is
possible
perform
in
an
effective,
scalable
yielding
manner.
After
applying
design
experiment
(DoE)
principles
mathematical
modelling,
most
parameter
set
could
be
identified,
leading
excellent
results
just
4
h
reaction
time:
isolated
yield
82
%
assay
ee
96
%.
Such
methods
can
serve
open
new
avenues
preparation
functional
molecules
on
both
small
industrially-relevant
scales.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(20)
Published: Jan. 29, 2024
To
facilitate
the
discovery
and
development
of
new
pharmaceuticals,
demand
for
novel
stereofunctionalised
building
blocks
has
never
been
greater.
Whilst
molecules
bearing
quaternary
tetrasubstituted
stereogenic
centres
are
ideally
suited
to
explore
untapped
areas
chemical
space,
asymmetric
construction
ofsterically
congested
carbon
remains
a
longstanding
challenge
in
organic
synthesis.
The
enantioselective
assembly
acyclic
is
even
more
demanding
due
need
restrict
much
wider
range
geometries
conformations
intermediates
involved.
In
this
context,
catalytic
allylicalkylation
(AAA)
prochiral
nucleophiles,
namely
enolates,
become
an
indispensable
tool
access
linearα-quaternary
andα-tetrasubstituted
carbonyl
compounds.
However,
unlike
AAA
cyclic
enolates
with
fixed
enolate
geometry,
achieve
high
levels
stereocontrol
stereoselectivity
enolisation
must
be
considered.
aim
review
offer
acomprehensivediscussion
reactions
their
analogues
generate
chiral
using
metal,
non-metal
dual
catalysis,
particular
focus
given
control
geometry
its
impact
on
stereochemical
outcome
reaction.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(10), P. 2870 - 2883
Published: Jan. 1, 2024
DFT
calculations
were
performed
to
investigate
palladium-catalyzed
decarboxylative
allylic
alkylation
of
allyl
difluoro-β-ketoesters.
The
synergistic
effects
ligand
and
fluorine
substituents
on
regioselectivity
uncovered.
Molecules,
Journal Year:
2025,
Volume and Issue:
30(3), P. 603 - 603
Published: Jan. 29, 2025
Enantiopure
turbo
chirality
in
small
organic
molecules,
without
other
chiral
elements,
is
a
fascinating
topic
that
has
garnered
significant
interest
within
the
chemical
and
materials
science
community.
However,
further
research
into
application
of
this
concept
have
been
severely
limited
by
lack
effective
asymmetric
tools.
To
date,
only
few
enantiomers
targets
isolated,
these
were
obtained
through
physical
separation
using
HPLC,
typically
on
milligram
scales.
In
work,
we
report
first
approach
to
enantiopure
absence
elements
such
as
central
axial
chirality.
This
demonstrated
assembling
aromatic
phosphine
oxides,
where
three
propeller-like
groups
are
anchored
P(O)
center
via
axes.
Asymmetric
induction
was
successfully
carried
out
sulfonimine
auxiliary,
with
absolute
configurations
conformations
unambiguously
determined
X-ray
diffraction
analysis.
The
resulting
frameworks
exhibit
propellers
arranged
either
clockwise
(P,P,P)
or
counterclockwise
(M,M,M)
configuration.
arrangements,
bulkier
sides
rings
oriented
toward
oxygen
atom
P=O
bond
rather
than
opposite
direction.
Additionally,
orientational
configuration
controlled
auxiliary
well,
showing
one
Naph
pushed
away
from
group
(-CH2-NHSO2-tBu)
phenyl
ring.
Computational
studies
conducted
relative
energies
for
rotational
barriers
target
along
axis
transition
pathway
between
two
enantiomers,
meeting
our
expectations.
work
expected
impact
fields
chemistry,
biomedicine,
future.
