ACS Catalysis,
Год журнала:
2024,
Номер
14(4), С. 2746 - 2757
Опубликована: Фев. 7, 2024
Remote
stereocontrol
in
transition-metal
catalysis
is
a
challenging
but
interesting
research
topic.
In
this
work,
we
achieved
copper-catalyzed
asymmetric
yne-allylic
substitution
using
electron-rich
arenes
and
acyclic
carbonates
through
remote
enantioselectivity
control.
The
reaction
delivers
variety
of
enantioenriched
products
that
contain
diverse
set
valuable
moieties,
such
as
conjugated
enynes,
indoles,
indolizines,
allenes,
dihydrofurans,
which
are
widely
used
organic
synthesis
act
key
units
bioactive
molecules
natural
products.
synthetic
value
protocol
has
been
demonstrated
series
further
transformations,
mechanistic
studies
have
conducted
to
gain
more
insight
into
the
reaction.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(46), С. 21347 - 21355
Опубликована: Ноя. 11, 2022
The
first
copper-catalyzed
enantioselective
[4
+
1]
annulation
of
yne-allylic
esters
with
1,3-dicarbonyl
compounds
was
realized
through
an
elegant
remote
stereocontrol
strategy.
very
ε
regioselective
nucleophilic
substitution
developed
by
employing
a
novel
chiral
copper-vinylvinylidene
species
from
the
new
C4
synthon
esters.
Thus,
greatly
diverse
spirocycles
were
obtained
ample
scope
and
excellent
levels
chemo-,
regio-,
enantioselectivities.
Moreover,
detailed
mechanistic
studies
suggest
Conia-ene
cascade
pathway
on
stereochemical
induction
progress.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(52)
Опубликована: Ноя. 13, 2023
Impressive
progress
has
been
made
in
the
copper-catalyzed
asymmetric
propargylic
substitution
(APS)
reaction,
but
its
use
remote
yne-allylic
remains
a
challenging
topic.
Herein,
we
report
first
enantioselective
sulfonylation
of
esters
with
sodium
sulfinates.
The
reaction
is
assumed
to
occur
via
copper-vinylvinylidene
species
as
key
reactive
intermediate.
readily
available
starting
materials,
mild
conditions,
and
excellent
regio-,
enantio-
stereoselectivity,
well
broad
substrate
scope
(>70
examples),
show
practicality
attractiveness
this
method.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(47)
Опубликована: Окт. 16, 2023
Abstract
Catalytic
asymmetric
transformations
by
dearomatization
have
developed
into
a
widely
applicable
synthetic
strategy,
but
heavily
relied
on
the
use
of
arenes
bearing
heteroatom.
In
this
case,
is
facilitated
involvement
p
‐orbital
electron
Different
from
conventional
substrate‐dependent
model,
here
we
demonstrate
that
activation
d
transition‐metal
center
can
serve
as
driving
force
for
dearomatization,
and
applied
to
development
novel
alkynyl
copper
remote
substitution
reaction.
A
newly
modified
PyBox
chiral
ligand
enables
construction
valuable
diarylmethyl
triarylmethyl
skeletons
in
high
enantioselectivities.
An
unexpected
tandem
process
involving
sequential
substitution/cyclization/1,5‐H
shift
leads
formation
enantioenriched
C−N
axis.
gram‐scale
reaction
various
downstream
highlight
robustness
method
potential
products.
Preliminary
mechanistic
studies
reveal
mononuclear
Cu‐catalyzed
process.
ACS Catalysis,
Год журнала:
2024,
Номер
14(12), С. 9244 - 9253
Опубликована: Июнь 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,
Год журнала:
2024,
Номер
14(12), С. 9254 - 9264
Опубликована: Июнь 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.
