Molecules,
Год журнала:
2023,
Номер
28(11), С. 4279 - 4279
Опубликована: Май 23, 2023
The
desymmetrization
of
N-pyrazolyl
maleimides
was
realized
through
an
asymmetric
Michael
addition
by
using
pyrazolones
under
mild
conditions,
leading
to
the
formation
a
tri-N-heterocyclic
pyrazole-succinimide-pyrazolone
assembly
in
high
yields
with
excellent
enantioselectivities
(up
99%
yield,
up
ee).
use
quinine-derived
thiourea
catalyst
essential
for
achieving
stereocontrol
vicinal
quaternary-tertiary
stereocenters
together
C-N
chiral
axis.
Salient
features
this
protocol
included
broad
substrate
scope,
atom
economy,
conditions
and
simple
operation.
Moreover,
gram-scale
experiment
derivatization
product
further
illustrated
practicability
potential
application
value
methodology.
ACS Catalysis,
Год журнала:
2024,
Номер
14(15), С. 11318 - 11331
Опубликована: Июль 15, 2024
Catalytic
enantioselective
borylation
reactions
of
unsaturated
bonds
as
powerful
tools
for
the
synthesis
diverse
chiral
organoboron
compounds
have
gained
much
attention
and
wide
applications
in
various
fields.
However,
atroposelective
arylboration
reaction
with
carbon–carbon
triple
1,3-enynes
to
obtain
axially
1,3-dienylboronates
remains
an
elusive
significant
challenge.
Hence,
we
develop
a
cooperative
copper-
palladium-catalyzed
assemble
plentiful
function
enriched
single
step
from
easily
available
1,3-enynes,
B2pin2,
aryl
bromides
high
levels
chemo-,
regio-,
stereo-,
atroposelectivity.
The
mild
conditions
lead
good
functional
group
tolerance,
which
is
proven
by
broad
substrate
scope
late-stage
functionalizations
bioactive
or
drug
molecules.
Moreover,
can
be
scaled
up,
series
further
transformations
achieved.
It
worth
emphasizing
that
several
olefin
catalysts
ligands
axial
chirality
also
synthesized
through
corresponding
elaborations
such
products,
explains
transformative
ability
application
potential
1,3-dienylboronates.
mechanism
experiment
density
theory
(DFT)
calculations
revealed
process
copper
palladium
catalysis,
indicating
chemoselectivity
regioselectivity
boration
are
determined
enyne
insertion
on
copper,
atroposelectivity
controlled
reductive
elimination
center.
Meanwhile,
calculation
demonstrated
distinct
interactions
between
P═O
C═O
groups
Pd
Bpin
center
key
transition
state
formation
products
varying
configurations
while
employing
identical
configuration
ligands.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(42), С. 29214 - 29223
Опубликована: Окт. 9, 2024
Macrocycles
incorporating
conformationally
defined
indoles
are
widely
found
in
bioactive
natural
products.
However,
the
catalytic
enantioselective
synthesis
of
planar-chiral
via
indolization
involving
macrocyclization
remains
elusive.
Herein,
we
present
first
rhodium(III)-catalyzed
atroposelective
macrocyclization,
which
involves
C-H
activation
aniline,
and
a
subsequent
oxidation
[3
+
2]
annulation
reaction
with
an
intramolecular
alkyne.
This
protocol
achieves
construction
indoles,
planar
chirality
control
single
step.
Importantly,
this
strategy
produces
macrocyclic
atropisomers
bearing
full-carbon
ansa
chains,
represent
challenging
targets
organic
synthesis.
Thermodynamic
experiments
revealed
that
rotational
barrier
chain-linked
atropisomer
was
lower
than
oxa-ansa
chain.
The
mechanism
elucidated
by
computational
studies,
alkyne
insertion
steps
collectively
determined
enantioselectivity.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 24, 2025
An
N-heterocyclic
carbene-catalyzed
atroposelective
[3
+
3]
annulation
of
alkynyl
acylazoliums
with
benzothiazole
derivatives
has
been
developed
for
the
divergent
synthesis
axially
chiral
triaryl
2-pyranones
and
fused
2-pyridones.
The
regioselectivity
this
protocol
depends
on
structure
benzothiazoles
three
different
nucleophilic
centers.
obtained
frameworks
represent
a
new
class
arylheterocycle
atropisomers,
which
may
be
potentially
useful
in
medicinal
chemistry.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(51)
Опубликована: Ноя. 3, 2023
Abstract
Planar‐chiral
cyclophanes
have
received
increasing
attention
for
drug
discovery
and
catalyst
design.
However,
the
catalytically
asymmetric
synthesis
of
planar‐chiral
has
been
a
longstanding
challenge.
We
describe
first
Pd(II)‐catalyzed
enantioselective
C−H
olefination
prochiral
cyclophanes.
The
low
rotational
barrier
less
hindered
benzene
ring
in
substrates
allows
reaction
to
proceed
through
dynamic
kinetic
resolution.
This
approach
exhibits
broad
substrate
scope,
providing
high
yields
(up
99
%)
with
excellent
enantioselectivities
>99
%
ee
).
ansa
chain
length
scope
studies
reveal
that
chirality
arises
from
bond
rotation
constraint
around
macrocycle
plane,
rather
than
C−N
axis.
activation
is
also
applicable
late‐stage
modification
bioactive
molecules
pharmaceuticals.
ACS Catalysis,
Год журнала:
2023,
Номер
13(21), С. 14155 - 14162
Опубликована: Окт. 20, 2023
Planar-chiral
cyclophanes
have
received
increasing
attention
for
drug
discovery
due
to
their
unique
properties
arising
from
the
conformational
strain.
However,
catalytic
asymmetric
synthesis
of
planar-chiral
is
one
long-standing
challenges
in
chemistry.
We
herein
report
a
Brønsted
acid-catalyzed
transfer
hydrogenation
(ATH)
reaction
cyclophane-derived
imines,
providing
good
yields
(up
98%)
and
with
high
enantioselectivities
>99%
ee).
The
mutable
ansa
bridge
allows
ATH
occur
through
kinetic
resolution
or
dynamic
process.
[11]–[14]cyclophanes
bearing
an
appropriate
benzene
ring
substituent
undergo
KR
process,
while
[15]–[17]cyclophanes
DKR
manner.
Controlled
experiments
were
performed
understand
mechanism
origin
enantioselectivity.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(25), С. 13581 - 13591
Опубликована: Июнь 14, 2023
The
resorcinol-terpene
phytocannabinoid
template
is
a
privileged
scaffold
for
the
development
of
diverse
therapeutics
targeting
endocannabinoid
system.
Axially
chiral
cannabinols
(axCBNs)
are
unnatural
(CBNs)
that
bear
an
additional
C10
substituent,
which
twists
cannabinol
biaryl
framework
out
planarity
creating
axis
chirality.
This
unique
structural
modification
hypothesized
to
enhance
both
physical
and
biological
properties
cannabinoid
ligands,
thus
ushering
in
next
generation
system
chemical
probes
cannabinoid-inspired
leads
drug
development.
In
this
full
report,
we
describe
philosophy
guiding
design
axCBNs
as
well
several
synthetic
strategies
their
construction.
We
also
introduce
second
class
axially
cannabinoids
inspired
by
cannabidiol
(CBD),
termed
cannabidiols
(axCBDs).
Finally,
provide
analysis
(axCannabinoid)
atropisomerism,
spans
two
classes
(class
1
3
atropisomers),
first
evidence
axCannabinoids
retain─and
some
cases,
strengthen─affinity
functional
activity
at
receptors.
Together,
these
findings
present
promising
new
direction
novel
ligands
discovery
exploration
complex