Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 17, 2024
Abstract
Chiral
tetrasubstituted
allenes
have
emerged
as
important
architectures
for
engineering
biologically
active
compounds.
The
construction
of
unique
allene
scaffolds
with
precise
control
continuous
central
and
axial
chirality
remains
yet
to
be
developed.
Here,
we
report
a
remote
enantioselective
ϵ‐alkylation
yne‐propargylic
acetates
enals
enabled
by
NHC
copper
cooperative
catalysis,
leading
series
excellent
enantioselectivities
(up
>99
%
ee)
diastereoselectivities
>95
:
5
dr).
This
method
features
high
regioselectivity
simultaneous
chirality.
Mechanistic
studies
suggest
activation
mode
synergistic
distal
created
from
the
ethynylallenylidenes.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(12), P. 9244 - 9253
Published: June 3, 2024
Catalytic
asymmetric
dearomatization
(CADA)
is
a
powerful
tool
for
the
rapid
construction
of
complex
chiral
three-dimensional
cyclic
molecules
featuring
quaternary
carbon
centers
from
readily
available
arenes.
However,
ubiquitous
nonfunctionalized
1-naphthols
to
afford
remains
challenging
and
undeveloped.
This
study
reports
dearomative
[4
+
1]
spiroannulation
via
copper
catalysis.
reaction
features
highly
chemo-,
regio-,
stereoselective
nucleophilic
addition
intramolecular
annulation
cascade
reactive
π-extended
copper-allenylidene,
thus
enabling
practical
synthesis
range
valuable
spirocyclic
enones
bearing
stereocenter
with
high
efficiency.
Furthermore,
this
protocol
applicable
phenols.
Control
experiments
supported
substitution-annulation
mechanism
by
excluding
process
involving
1,3-sigmatropic
shift.
Preliminary
biological
activity
studies
indicated
that
synthesized
hold
significant
promise
as
anticancer
agents
inducing
tumor
cell
apoptosis.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(12), P. 9254 - 9264
Published: June 3, 2024
Catalytic
asymmetric
dearomatization
reactions
of
α-unsubstituted
β-naphthols
are
very
challenging
due
to
the
high
energy
barrier
resulting
from
loss
aromaticity.
Herein,
we
describe
an
example
enantioselective
catalytic
dearomative
spiroannulation
with
yne-allylic
esters.
The
success
this
reaction
relied
on
copper-catalyzed
remote
strategy
using
esters
as
bis-electrophilic
reagents.
This
transformation
features
mild
conditions,
broad
functional
group
tolerance,
and
extensive
substrate
scope,
thereby
facilitating
efficient
construction
array
enantioenriched
naphthalene-2-one
spiroindolenine
derivatives.
Experimental
studies
density
theory
calculations
establish
pathway
origin
stereoselectivity.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(27), P. 5758 - 5763
Published: July 1, 2024
Anthrones
are
key
structural
motifs
in
many
natural
products
and
pharmaceutical
chemicals.
However,
due
to
its
unique
tricyclic
aromatic
structure,
the
synthetic
space
for
development
of
chiral
anthrone
derivatives
is
largely
limited.
By
utilizing
potential
copper-catalyzed
remote
asymmetric
yne-allylic
substitution
reaction,
we
describe
first
example
highly
regio-
enantioselective
on
various
esters
with
anthrones
under
a
mild
reaction
condition,
which
afforded
range
enantioenriched
1,3-enynes
exhibiting
broad
functional
group
tolerance
across
51
examples.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Aug. 10, 2024
The
construction
of
atropisomers
with
1,2-diaxes,
while
maintaining
high
enantiocontrol,
presents
a
significant
challenge
due
to
the
dynamic
nature
steric
hindrance
at
ortho-aryl
substituents.
Although
various
catalytic
asymmetric
methods
have
been
developed
for
accessing
axially
chiral
arylpyrroles,
synthesis
arylpyrroles
1,2-diaxes
in
manner
has
remained
rare.
Herein,
authors
report
diverse
and
C-C
C-N
axes
through
copper-catalysed
asymmetirc
[4
+
1]
annulation
yne-allylic
esters
arylamines
via
remote
stereocontrol
strategy.
This
approach
provides
facile
access
broad
range
heterobiaryl
(67
examples)
excellent
enantioselectivities,
each
bearing
one
or
two
C-C/C-N
axes,
demonstrating
its
versatility
efficiency.
utility
this
methodology
is
further
highlighted
by
transformation
product
into
phosphine
ligand,
thioureas
use
catalysis.
Synlett,
Journal Year:
2024,
Volume and Issue:
unknown
Published: March 25, 2024
Abstract
Two
novel
copper-catalyzed
cyclization
reactions
involving
a
remote
propargylic
substitution/cyclization/isomerization
cascade
are
disclosed.
Derivatives
of
the
seldomly
studied
heterocycles
thieno[2,3-c]pyrrole
and
thieno[2,3-d]pyridazine
conveniently
synthesized
in
moderate
to
good
yields
from
primary
amines
or
arylhydrazines
through
[4+1]
[4+2]
reactions,
respectively.
Preliminary
mechanistic
experiments
corroborated
occurrence
designed
reactions.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(28), P. 5961 - 5965
Published: July 10, 2024
Chiral
coumarins
and
their
derivatives
are
prominent
bioactive
structural
units
present
in
a
wide
range
of
natural
products
pharmaceutical
candidates.
Therefore,
the
development
straightforward
efficient
methodologies
for
synthesis
readily
functionalized
chiral
is
significant
interest.
Herein
we
report
an
enantioselective
copper-catalyzed
yne-allylic
substitution
coumarins,
resulting
highly
regioselective
diverse
new
classes
coumarin
with
high
efficiency
excellent
functional
group
tolerance.
Subsequent
versatile
transformations
further
demonstrate
substantial
synthetic
potential
this
strategy
field
biochemical
research.
