Dynamic Kinetic Resolution-Based Asymmetric Transfer Hydrogenation of Racemic 2-Substituted Quinolines
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 22, 2025
The
synthesis
of
chiral
tetrahydroquinolines
(THQs)
has
garnered
significant
interest
from
medicinal
chemists
due
to
their
frequent
presence
as
pharmacophores
in
bioactive
compounds.
While
existing
synthetic
methods
have
primarily
focused
on
THQs
with
single
or
multiple
endocyclic
centers,
the
selective
construction
both
endo-
and
exo-cyclic
centers
remains
a
challenge
that
requires
further
development.
This
study
introduces
dynamic
kinetic
resolution
(DKR)-based
transfer
hydrogenation
racemic
2-substituted
quinolines,
which
yields
structurally
novel
consecutive
excellent
stereoselectivities
(59
examples,
generally
>20:1
dr
>90%
ee,
up
three
stereocenters).
Our
approach
offers
mechanistically
method
for
asymmetric
transformation
electron-deficient
aromatic
N-heterocycles
presents
an
innovative
way
expand
N-heterocycle
chemical
space
chemistry.
Язык: Английский
A meta-learning approach for selectivity prediction in asymmetric catalysis
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Апрель 15, 2025
Abstract
Transition
metal-catalyzed
asymmetric
reactions
are
of
high
contemporary
importance
in
organic
synthesis.
Recently,
machine
learning
(ML)
has
shown
promise
accelerating
the
development
newer
catalytic
protocols.
However,
need
for
large
amount
experimental
data
can
present
a
bottleneck
implementing
ML
models.
Here,
we
propose
meta-learning
workflow
that
harness
literature-derived
to
extract
shared
reaction
features
and
requires
only
few
examples
predict
outcome
new
reactions.
Prototypical
networks
used
as
method
enantioselectivity
hydrogenation
olefins.
This
model
consistently
provides
significant
performance
improvement
over
other
popular
methods
such
random
forests
graph
neural
networks.
The
our
meta-model
is
analyzed
with
varying
sizes
training
demonstrate
its
utility
even
limited
data.
A
good
on
an
out-of-sample
test
set
further
indicates
general
applicability
approach.
We
believe
this
work
will
provide
leap
forward
identifying
promising
early
phases
when
minimal
available.
Язык: Английский
Iridium-Catalyzed Asymmetric Hydrogenation of Unfunctionalized Cycloalkenes to Access Chiral 2-Aryl Tetralins
Organic Letters,
Год журнала:
2024,
Номер
26(27), С. 5850 - 5855
Опубликована: Июль 1, 2024
The
transition-metal
catalyzed
asymmetric
hydrogenation
of
unfunctionalized
alkenes
is
challenging.
Herein,
we
report
an
efficient
iridium-catalyzed
cycloalkenes,
delivering
chiral
2-aryl
tetralins
in
excellent
yields
and
with
moderate
to
enantioselectivities.
reaction
can
be
performed
on
a
gram-scale
low
catalyst
loading
(S/C
=
1000),
the
reduced
product
was
obtained
without
erosion
enantioselectivity.
Deuterium
experiments
indicated
that
C═C
bond
substrate
hydrogenated
directly
isomerization.
Язык: Английский
Synthesis and applications of optically pure trans-2-(3,5-dimethylphenoxy)cyclohexan-1-ol as chiral auxiliary for preparation of α-substituted carboxylic acid derivatives
Tetrahedron,
Год журнала:
2024,
Номер
unknown, С. 134326 - 134326
Опубликована: Окт. 1, 2024
Язык: Английский
Enantioselective Synthesis of Chiral β2-Amino Phosphorus Derivatives via Nickel-Catalyzed Asymmetric Hydrogenation
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 27, 2024
Compared
with
chiral
β3-amino
phosphorus
compounds,
which
can
be
easily
derived
from
natural
optically
pure
α-amino
acids,
obtaining
β2-amino
derivatives
remains
a
challenge.
These
derivatives,
cannot
amino
possess
unique
biological
activities
or
potential
catalytic
activities.
Herein,
highly
enantioselective
hydrogenation
for
the
preparation
of
E-β-enamido
compounds
is
reported
by
using
green
and
low-cost
earth-abundant
metal
nickel
catalyst
(13
examples
99%
ee).
In
particular,
this
system
provides
same
enantiomer
product
E-
Z-alkene
substrates,
E/Z-substrate
mixtures
provide
good
results
(up
to
96%
The
products
diversely
derivatized,
exhibit
as
novel
β2-aminophosphine
ligands.
Density
functional
theory
calculations
reveal
that
weak
attractive
interactions
between
substrate
are
crucial
achieving
perfect
enantioselectivities.
addition,
different
coordination
modes
Z-substrates
may
result
in
formation
product.
Язык: Английский
A New Dynamic Kinetic Resolution Strategy for Asymmetric Hydrogenation of Indoles
Chinese Journal of Organic Chemistry,
Год журнала:
2024,
Номер
44(4), С. 1374 - 1374
Опубликована: Янв. 1, 2024
Язык: Английский
Dynamic Kinetic Resolution of Racemic 2-Substituted Indoles by Pd-Catalyzed Asymmetric Hydrogenation
Synfacts,
Год журнала:
2024,
Номер
20(06), С. 0604 - 0604
Опубликована: Май 14, 2024
Key
words
dynamic
kinetic
resolution
-
hydrogenation
indoles
indolines
palladium
catalysis
vicinal
stereogenic
centers
Язык: Английский
Construction of Chiral C2-Quaternary Indolines via Palladium-Catalyzed Decarboxylative Asymmetric Amination
ACS Catalysis,
Год журнала:
2024,
Номер
15(1), С. 255 - 264
Опубликована: Дек. 16, 2024
The
catalytic
asymmetric
synthesis
of
functionalized
C2-quaternary
indoline
scaffolds
has
garnered
significant
attention
in
organic
and
drug
discovery
due
to
the
inherent
challenges
potential
applications.
Herein,
we
present
a
facile
approach
utilizing
Pd-catalyzed
intramolecular
decarboxylative
amination
vinyl
benzoxazepinones,
leading
efficient
construction
challenging
chiral
2-vinyl-2-aryl/alkyl
frameworks
good
yields
with
high
enantioselectivities
(>50
examples,
up
83%
yield
97%
ee).
Furthermore,
these
indolines
can
be
readily
scaled
further
modified
access
complex
polycyclic
structures.
We
also
synthesized
several
indoline-based
ligands
that
exhibit
promising
efficiency
as
catalysts
reactions.
Computational
studies
provided
insight
into
inner-sphere
mechanism.
Язык: Английский