Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Авг. 23, 2024
Atropisomeric
biaryls
bearing
carbonyl
groups
have
attracted
increasing
attention
due
to
their
prevalence
in
diverse
bioactive
molecules
and
crucial
role
as
efficient
organo-catalysts
or
ligands
asymmetric
transformations.
However,
preparation
often
involves
tedious
multiple
steps,
the
direct
synthesis
via
carbonylation
has
scarcely
been
investigated.
Herein,
we
report
an
palladium-catalyzed
enantioconvergent
aminocarbonylation
of
racemic
heterobiaryl
triflates
with
amines
dynamic
kinetic
transformation
(DyKAT).
This
protocol
features
a
broad
substrate
scope
excellent
compatibility
for
rapid
construction
axially
chiral
amides
good
high
yields
enantioselectivities.
Detailed
mechanistic
investigations
discover
that
base
can
impede
intramolecular
hydrogen
bond-assisted
axis
rotation
products,
thus
allowing
success
achieve
enantioselectivity.
Moreover,
achieved
be
directly
utilized
N,N,N-pincer
copper-catalyzed
enantioselective
formation
C(sp3)-N
C(sp3)-P
bonds.
Axially
containing
not
only
exist
various
drug
candidates
but
also
serve
authors
transformation.
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 1147 - 1157
Опубликована: Янв. 3, 2025
This
study
describes
a
photoredox/cobalt
dual-catalyzed
asymmetric
Grignard-type
addition
reaction,
enabling
the
synthesis
of
axially
chiral
hexatomic
(six–six)
N-heterobiaryls
bearing
extra
secondary
alcohol
unit
via
an
efficient
dynamic
kinetic
transformation
racemic
N-heterobiaryl
triflate
substrates.
The
conversion
facilitated
both
photoredox
and
classical
reductive
reaction
conditions
exhibits
good
functional
group
tolerance,
broad
substrate
scope,
satisfactory
stereoselectivity.
Furthermore,
control
experiments
density
theory
calculations
provide
preliminary
mechanistic
insights.
Precision Chemistry,
Год журнала:
2024,
Номер
2(5), С. 208 - 220
Опубликована: Апрель 23, 2024
The
catalytic
asymmetric
diastereodivergent
synthesis
of
axially
chiral
2-alkenylindoles
was
established
via
phosphoric
acid-catalyzed
addition
reactions
C3-unsubstituted
with
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(22), С. 11165 - 11206
Опубликована: Янв. 1, 2024
This
review
explores
the
fascinating
world
of
molecules
featuring
multiple
stereogenic
elements,
unraveling
different
strategies
designed
over
years
for
their
enantioselective
synthesis.
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 4638 - 4647
Опубликована: Март 12, 2024
Axially
chiral
diaryl
ethers
make
up
a
unique
class
of
atropisomers
bearing
restricted
rotation
about
the
C–O
bond.
Methods
for
expedient
synthesis
axially
ether-based
structures
have
been
largely
underdeveloped.
Herein,
we
developed
an
efficient
metal-catalyzed
desymmetrization
strategy
to
unveil
formation
and
centrally
dual
in
high
diastereo-
enantioselectivity.
The
protocol
leverages
cobalt-catalyzed
photoreductive
enantioselective
couplings
dialdehyde
alkyne
deliver
stereogenicity,
ether
scaffold
is
equipped
with
useful
synthetic
handles
including
formyl,
hydroxyl,
allyl
groups,
as
has
demonstrated
carboxylic
acid
potential
ligand
asymmetric
catalysis.
ACS Catalysis,
Год журнала:
2024,
Номер
14(9), С. 6965 - 6972
Опубликована: Апрель 18, 2024
The
synthesis
of
N–N
axially
chiral
molecules
in
the
enantiopure
form
has
emerged
as
an
interesting
research
topic
primarily
due
to
significance
and
intricacy
synthesizing
these
molecules,
especially
bearing
heterocyclic
motifs.
Herein,
we
disclose
a
method
for
introduction
axial
chirality
along
with
point
center
via
N-heterocyclic
carbene
(NHC)-catalyzed
atroposelective
dihydropyridinone-containing
indoles
pyrroles.
reaction
follows
(3
+
3)
annulation
approach
by
interception
indole/pyrrole-derived
enamines
α,β-unsaturated
aldehydes
under
oxidative
NHC
catalysis
proceeding
acylazoliums.
indoles/pyrroles
were
formed
mild
conditions
broad
scope
high
selectivity.
In
addition,
preliminary
DFT
studies
rotational
barrier
products
performed.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(6), С. 4067 - 4073
Опубликована: Фев. 23, 2024
We
describe
herein
an
N-heterocyclic-carbene-catalyzed
atroposelective
synthesis
of
axially
chiral
diaryl
ethers.
Through
a
sequentially
enantioselective
desymmetric
process
and
kinetic
resolution
process,
the
products
could
be
constructed
in
good
yields
with
excellent
enantiopurities.
Both
alcohols
phenols
were
compatible
this
catalytic
system.
The
carboxylic
acids
derived
from
esters
proven
to
potential
ligands
for
asymmetric
synthesis,
example,
Rh(III)-catalyzed
C–H
functionalization.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(10)
Опубликована: Янв. 10, 2024
Stereodivergent
engineering
of
one
enzyme
to
create
stereocomplementary
variants
for
synthesizing
optically
pure
molecules
with
tailor-made
(R)
or
(S)
configurations
on
an
optional
basis
is
highly
desirable
and
challenging.
This
study
aimed
engineer
fatty
acid
photodecarboxylase
from
Chlorella
variabilis
(CvFAP)
using
the
focused
rational
iterative
site-specific
mutagenesis
(FRISM)
strategy
obtain
two
excellent
selectivity
(both
giving
products
up
99
%
e.e.).
These
were
used
CvFAP-catalyzed
light-driven
kinetic
resolution
oxalates
oxamic
acids
prepared
corresponding
sec-alcohols
amines,
providing
a
new
biotransformation
process
preparing
chiral
amines.
Molecular
dynamics
simulation,
data
transient
spectra
revealed
source
selectivity.
represents
first
example
amines
catalyzed
by
pair
CvFAPs.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(30)
Опубликована: Май 15, 2024
Atropisomers
hold
significant
fascination,
not
only
for
their
prevalence
in
natural
compounds
but
also
biological
importance
and
wide-ranging
applications
as
chiral
materials,
ligands,
organocatalysts.
While
biaryl
heterobiaryl
atropisomers
are
commonly
studied,
the
enantioselective
synthesis
of
less
abundant
heteroatom-linked
non-biaryl
presents
a
formidable
challenge
modern
organic
synthesis.
Unlike
classical
atropisomers,
these
molecules
allow
rotation
around
two
bonds,
resulting
low
barriers
to
enantiomerization
through
concerted
bond
rotations.
In
recent
years
discovery
new
configurationally
stable
rare
scaffolds
such
aryl
amines,
ethers
sulfones
well
innovative
methodologies
control
configuration
have
been
disclosed
literature
constitute
topic
this
minireview.
