European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 29, 2024
Abstract
Axially
chiral
biaryl
aldehydes
are
precursors
for
the
synthesis
of
axially
compounds
and
novel
catalysts
great
interest,
which
play
vital
roles
in
extensive
research
fields.
However,
limited
strategies
exist
efficient
aldehydes,
construction
structurally
diverse
remains
challenging.
Herein,
a
strategy
is
reported
with
varying
structures
from
dialdehydes
aromatic
amines
presence
phosphoric
acid
catalyst.
This
protocol
features
excellent
enantioselectivity,
mild
conditions,
good
functional‐group
tolerance.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(41)
Опубликована: Июль 17, 2024
Axially
chiral
biaryl
compounds
are
ubiquitous
scaffolds
in
natural
products,
bioactive
molecules,
ligands
and
catalysts,
but
biocatalytic
methods
for
their
asymmetric
synthesis
limited.
Herein,
we
report
a
highly
efficient
route
the
atroposelective
of
biaryls
by
dynamic
kinetic
resolution
(DKR).
This
DKR
approach
features
transient
six-membered
aza-acetal-bridge-promoted
racemization
followed
an
imine
reductase
(IRED)-catalyzed
stereoselective
reduction
to
construct
axial
chirality
under
ambient
conditions.
Directed
evolution
IRED
from
Streptomyces
sp.
GF3546
provided
variant
(S-IRED-Ss-M11)
capable
catalyzing
process
access
variety
aminoalcohols
high
yields
excellent
enantioselectivities
(up
98
%
yield
>99
:
1
enantiomeric
ratio).
Molecular
dynamics
simulation
studies
on
S-IRED-Ss-M11
revealed
origin
its
improved
activity
atroposelectivity.
By
exploiting
substrate
promiscuity
IREDs
power
directed
evolution,
our
work
further
extends
biocatalysts'
toolbox
challenging
axially
molecules.
Living
biological
systems
rely
on
the
continuous
operation
of
chemical
reaction
networks.
These
networks
sustain
out-of-equilibrium
regimes
in
which
energy
is
continually
converted
into
controlled
mechanical
work
and
motion.
Out-of-equilibrium
have
also
enabled
design
successful
development
artificial
autonomously
operating
molecular
machines,
comprising
pairs
formally—but
non-microscopically—reverse
pathways
drive
motion
at
level.
In
systems,
concurrent
multiple
by
chemoselectivity
enzymes
their
co-factors,
nature’s
dissipative
involve
several
classes
reactions.
contrast,
reactivity
that
has
been
harnessed
to
develop
pursuit
machines
limited
a
single
type.
Only
small
number
synthetic
exhibit
chemically
fuelled
molecular-level
motion,
all
exploit
same
class
acylation–hydrolysis
reaction.
Here
we
show
redox
network,
oxidation
reduction
pathways,
can
autonomous
unidirectional
about
C–C
bond
most
structurally
simple
motor
yet
reported,
an
achiral
biphenyl.
The
combined
use
oxidant
reductant
as
fuels,
directionality
motor,
are
both
exploiting
enantioselectivity
functional
separation
inherent
enzyme
catalysis.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 21, 2024
A
ligand-controlled
regiodivergent
and
enantioselective
ring
expansion
of
benzosilacyclobutenes
with
internal
naphthyl
alkynes
has
been
achieved
by
adjusting
the
ligand
cavity
size.
The
(
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 9, 2025
The
chemoenzymatic
dynamic
kinetic
resolution
of
2-(quinolin-8-yl)benzylalcohols
using
a
combination
lipases
and
ruthenium
catalysts
is
described.
While
CalB
lipase
performs
highly
selective
enzymatic
resolution,
the
with
Shvo's
or
Bäckvall's
promotes
atropisomerization
substrate
via
reversible
formation
configurationally
labile
aldehydes,
thereby
enabling
resolution.
This
synergistic
approach
was
applied
to
synthesis
variety
heterobiaryl
acetates
in
excellent
yields
enantioselectivities.
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.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(37)
Опубликована: Июнь 25, 2024
A
ruthenium-catalyzed
reductive
amination
via
asymmetric
transfer
hydrogenation
(ATH)
has
been
used
to
perform
an
efficient
dynamic
kinetic
resolution
(DKR)
of
N-aryl
2-formyl
pyrroles
decorated
with
a
phosphine
moiety
positioned
at
the
ortho'
position.
The
strategy
relies
on
labilization
stereogenic
axis
in
substrate
facilitated
by
transient
Lewis
acid-base
interaction
(LABI)
between
carbonyl
carbon
and
phosphorus
center.
reaction
features
broad
scope
aliphatic
amines
pyrrole
scaffolds,
proceeds
under
very
mild
conditions
afford
P,N
atropisomers
good
high
yields
excellent
enantioselectivities
(up
99
%
ee)
for
both
diphenyl
dicyclohexylphosphino
derivatives.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(41)
Опубликована: Июль 17, 2024
Abstract
Axially
chiral
biaryl
compounds
are
ubiquitous
scaffolds
in
natural
products,
bioactive
molecules,
ligands
and
catalysts,
but
biocatalytic
methods
for
their
asymmetric
synthesis
limited.
Herein,
we
report
a
highly
efficient
route
the
atroposelective
of
biaryls
by
dynamic
kinetic
resolution
(DKR).
This
DKR
approach
features
transient
six‐membered
aza‐acetal‐bridge‐promoted
racemization
followed
an
imine
reductase
(IRED)‐catalyzed
stereoselective
reduction
to
construct
axial
chirality
under
ambient
conditions.
Directed
evolution
IRED
from
Streptomyces
sp
.
GF3546
provided
variant
(
S
‐IRED‐
Ss
‐M11)
capable
catalyzing
process
access
variety
aminoalcohols
high
yields
excellent
enantioselectivities
(up
98
%
yield
>99
:
1
enantiomeric
ratio).
Molecular
dynamics
simulation
studies
on
‐M11
revealed
origin
its
improved
activity
atroposelectivity.
By
exploiting
substrate
promiscuity
IREDs
power
directed
evolution,
our
work
further
extends
biocatalysts’
toolbox
challenging
axially
molecules.
