Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 17, 2024
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,
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.
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.
Organic Letters,
Год журнала:
2024,
Номер
26(31), С. 6652 - 6657
Опубликована: Июль 26, 2024
We
report
a
visible-light-promoted
cyclization/sulfonylation
cascade
of
N-heterocycles
with
thianthrenium
salts
using
DABSO
as
the
SO2
surrogate.
This
method
features
excellent
functional
group
tolerance,
wide
substrate
scope,
and
late-stage
elaboration
bioactive
relevant
molecules.
Mechanistic
investigations
reveal
that
photoactive
electron
donor–acceptor
(EDA)
complexes
between
DABCO
are
capable
generation
aryl
radicals,
which
induce
following
insertion
by
attacking
DABSO,
thus
triggering
key
radical
cyclization
step.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(25), С. 16996 - 17002
Опубликована: Июнь 14, 2024
A
highly
regio-
and
enantioselective
hydrosulfonylation
using
commercially
available
sodium
sulfinates
is
reported,
providing
the
first
direct
asymmetric
rhodium-catalyzed
of
allenes/alkynes
to
synthesize
chiral
allylic
sulfones.
Ligand
screening
studies
demonstrated
indispensable
role
C1-symmetric
P,N-ligand
(Rax,S,S)-StackPhim
for
achieving
both
high
regioselecitivity
(>20:1)
enantioselectivity
(up
97%
ee).
Notably,
operationally
simple
method
mild
conditions
allow
rapid
preparation
sulfones
with
a
wide
scope
functional
groups.
Moreover,
use
tert-butyldimethylsilyloxymethanesulfinate
enables
collective
synthesis
various
sulfone
derivatives
after
transformations
protected
hydroxymethyl
product.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Авг. 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.
Organic Letters,
Год журнала:
2024,
Номер
26(27), С. 5758 - 5763
Опубликована: Июль 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.
