Controlling Stereoselectivity with Noncovalent Interactions in Chiral Phosphoric Acid Organocatalysis
Chemical Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 18, 2025
Chiral
phosphoric
acids
(CPAs)
have
emerged
as
highly
effective
Brønsted
acid
catalysts
in
an
expanding
range
of
asymmetric
transformations,
often
through
novel
multifunctional
substrate
activation
modes.
Versatile
and
broadly
appealing,
these
benefit
from
modular
tunable
structures,
compatibility
with
additives.
Given
the
unique
types
noncovalent
interactions
(NCIs)
that
can
be
established
between
CPAs
various
reactants─such
hydrogen
bonding,
aromatic
interactions,
van
der
Waals
forces─it
is
unsurprising
catalyst
systems
become
a
promising
approach
for
accessing
diverse
chiral
product
outcomes.
This
review
aims
to
provide
in-depth
exploration
mechanisms
by
which
impart
stereoselectivity,
positioning
NCIs
central
feature
connects
broad
spectrum
catalytic
reactions.
Spanning
literature
2004
2024,
it
covers
nucleophilic
additions,
radical
atroposelective
bond
formations,
highlighting
applicability
CPA
organocatalysis.
Special
emphasis
placed
on
structural
mechanistic
features
govern
CPA-substrate
well
tools
techniques
developed
enhance
our
understanding
their
behavior.
In
addition
emphasizing
details
stereocontrolling
elements
individual
reactions,
we
carefully
structured
this
natural
progression
specifics
broader,
class-level
perspective.
Overall,
findings
underscore
critical
role
catalysis
significant
contributions
advancing
synthesis.
Язык: Английский
Dynamic kinetic resolution and dynamic kinetic asymmetric transformation of atropisomeric biaryls
Chem Catalysis,
Год журнала:
2025,
Номер
unknown, С. 101329 - 101329
Опубликована: Март 1, 2025
Язык: Английский
Development of Configurationally Labile Biaryl Reagents for Atropisomer Synthesis
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(28)
Опубликована: Май 16, 2024
Abstract
Axially
chiral
biaryl
scaffolds
are
important
in
pharmaceuticals,
natural
products,
and
asymmetric
synthesis.
Atroposelective
ring‐opening
of
configurationally
labile
reagents
via
dynamic
kinetic
transformation
provides
a
valuable
approach
to
access
axially
atropisomers.
This
review
summarizes
seminal
contributions
recent
advancements
on
this
topic
based
the
use
different
types
reagents.
Язык: Английский
Lewis Acid‐Base Interactions as a Racemization Strategy for the Atroposelective Synthesis of (Hetero)biaryls via Dynamic Kinetic Resolution
ChemCatChem,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 8, 2024
Abstract
Due
to
their
molecular
topology,
atropisomers
serve
as
highly
valuable
chiral
frameworks
for
diverse
applications
across
academic
research
and
industry.
Despite
the
availability
of
numerous
established
catalytic
methods
synthesis,
there
is
still
a
high
demand
development
novel
resourceful
strategies.
In
this
concept
article,
we
will
detail
our
studies
on
use
transient
Lewis
acid‐base
interactions
(LABI)
dynamization
strategy
synthesis
(hetero)biaryl
by
Dynamic
Kinetic
Resolution
(DKR).
The
formation
cyclic
transition
states,
resulting
from
interaction
between
an
acidic
functionality
basic
counterpart,
plays
key
role
in
facilitating
racemization
substantially
reducing
barrier
atropisomerization.
scenario,
have
employed
transformations
aimed
at
neutralizing
nature
acid,
ultimately
leading
configurationally
stable
enantioenriched
compounds.
design
substrates
employment
stereoselective
strategies
based
metal
biocatalysis
resolution
detailed.
Specific
emphasis
preparation
axially
motifs
commonly
found
catalysis
or
medicinal
chemistry
also
be
given.
Язык: Английский
Symmetric Anion Mediated Dynamic Kinetic Asymmetric Knoevenagel Reaction for N−C and N−N Atropisomers Synthesis
Hongyu Qu,
Chenyang Huo,
Jimeng Ge
и другие.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 21, 2024
A
symmetric
anion
mediated
dynamic
kinetic
asymmetric
Knoevenagel
reaction
was
established
as
a
general
and
efficient
method
for
accessing
both
N-C
N-N
atropisomers.
The
resulting
highly
enantio-pure
pyridine-2,6(1H,3H)-diones
exhibit
diverse
structures
functional
groups.
key
to
excellent
regio-
remote
enantiocontrol
could
be
owed
the
hydrogen
bond
between
enolate
triflamide
block
of
organocatalyst.
This
connected
iminium
cation
by
chiral
backbone.
mechanism
investigation
via
control
experiments,
correlation
analysis,
density
theory
calculations
further
revealed
how
stereochemical
information
transferred
from
catalyst
into
axially
pyridine-2,6(1H,3H)-diones.
synthetic
applications
also
demonstrated
reaction's
potential.
Язык: Английский
Atroposelective biocatalysis employing alcohol dehydrogenases
Methods in enzymology on CD-ROM/Methods in enzymology,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Язык: Английский
Manganese-Catalyzed Asymmetric Hydrogenation for Atroposelective Dynamic Kinetic Resolution of Heterobiaryl Ketone N-Oxides
ACS Catalysis,
Год журнала:
2024,
Номер
unknown, С. 17633 - 17641
Опубликована: Ноя. 15, 2024
An
atroposelective
dynamic
kinetic
resolution
of
configurationally
labile
heterobiaryl
ketone
N-oxides
via
Mn-catalyzed
asymmetric
hydrogenation
has
been
disclosed.
By
use
a
structurally
finely
tuned
chiral
ferrocenyl
P,N,N-ligand,
the
proceeds
smoothly
under
mild
conditions
with
simultaneous
installation
central
and
axial
chirality,
giving
wide
range
atropisomeric
1-arylisoquinoline
2-arylpyridine
bearing
alcohol
structure
high
diastereo-
enantioselectivities.
The
diastereomer
product
could
be
readily
prepared
in
stereospecific
way
complete
inversion
chirality
Mitsunobu
reaction.
value
this
central-
axial-chiral
N-oxide
scaffold
is
preliminarily
demonstrated
by
its
successful
utility
as
catalyst
allylation
benzaldehyde
allyltrichlorosilane.
Язык: Английский
Symmetric Anion Mediated Dynamic Kinetic Asymmetric Knoevenagel Reaction for N−C and N−N Atropisomers Synthesis
Hongyu Qu,
Chenyang Huo,
Jimeng Ge
и другие.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(39)
Опубликована: Июль 3, 2024
Abstract
A
symmetric
anion
mediated
dynamic
kinetic
asymmetric
Knoevenagel
reaction
was
established
as
a
general
and
efficient
method
for
accessing
both
N−C
N−N
atropisomers.
The
resulting
highly
enantio‐pure
pyridine‐2,6(1
H
,3
)‐diones
exhibit
diverse
structures
functional
groups.
key
to
excellent
regio‐
remote
enantiocontrol
could
be
owed
the
hydrogen
bond
between
enolate
triflamide
block
of
organocatalyst.
This
connected
iminium
cation
by
chiral
backbone.
mechanism
investigation
via
control
experiments,
correlation
analysis,
density
theory
calculations
further
revealed
how
stereochemical
information
transferred
from
catalyst
into
axially
)‐diones.
synthetic
applications
also
demonstrated
reaction's
potential.
Язык: Английский