Angewandte Chemie,
Год журнала:
2024,
Номер
136(39)
Опубликована: Июнь 26, 2024
Abstract
Non‐directed
regioselective
activation
of
bis(boronic
esters),
followed
by
functionalization,
is
reported.
A
bulky
activator
shown
to
selectively
activate
the
less
hindered
boronic
ester
enabling
it
undergo
stereospecific
cross‐coupling
a
variety
electrophiles.
This
steric‐based
regioselectivity
provides
simple
and
efficient
method
prepare
highly
functionalized,
enantiomerically
enriched
products
starting
from
alkenes.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 8, 2025
Comprehensive
Summary
Herein,
we
present
the
first
examples
of
asymmetric
reductive
1,4‐dicarbofunctionalization
1,3‐dienes
and
1,5‐dicarbofunctionalization
vinylcyclopropanes,
which
proceed
under
catalysis
a
chiral
nickel/bis‐imidazoline
complex
using
alkyl
halides
aryl
iodides
or
alkenyl
bromides
as
electrophilic
coupling
partners.
In
these
highly
enantioselective
transformations
operating
in
radical
relay
mechanism,
C(sp
3
)‐
2
)‐type
carbo‐moieties
are
respectively
installed
on
terminal
internal
position
with
newly
formed
olefinic
unit
high
E
‐selectivity.
Advanced Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 5, 2024
A
Pd-catalyzed
enantioselective
aminosilylation
of
alkenes
via
tandem
Aza-Heck/silylation
reaction
under
Pd/Sadphos
catalysis
is
disclosed.
wide
array
oxime
esters
and
silicon
reagents
are
tolerated,
furnishing
the
chiral
pyrrolines
bearing
one
quaternary
or
two
contiguous
stereocenters
in
good
yield
with
high
enantioselectivity.
Not
only
terminal
but
also
tri-substituented
internal
successfully
participate
reaction,
delivering
vicinal
complete
diastereoselectivity
DFT
study
conducted
to
probe
pathway
origin
enantioselectivity,
which
revealed
that
stereoinduction
arises
from
weak
interaction
between
aromatic
ring
substrate
fragment
naphthyl
group
ligand.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 13, 2024
Non-directed
regioselective
activation
of
bis(boronic
esters),
followed
by
functionalization,
is
reported.
A
bulky
activator
shown
to
selectively
activate
the
less
hindered
boronic
ester
enabling
it
undergo
stereospecific
cross-coupling
a
variety
electrophiles.
This
steric-based
regioselectivity
provides
simple
and
efficient
method
prepare
highly
functionalized,
enantiomerically
enriched
products
starting
from
alkenes.
Here,
an
alcohol-directed
1,2-dicarbofunctionalization
of
alkenyl
alcohols
has
been
realized
with
aryl/alkenyl
boronic
acids
and
alkyl
halides
as
the
coupling
partners.
This
reaction
was
enabled
by
a
commercially
available
bulky
3-amyl
β-diketone
(Amacac)
ligand,
that
enhancing
reactivity
suppressing
many
competitive
processes.
With
alcohol
weak
native
directing
group,
this
protocol
delivers
1,2-arylalkylated
1,2-alkenylalkylated
high
efficiency,
regioselectivities,
broad
substrate
scope,
exceptional
functional
group
tolerance.
Notably,
methodology
facilitates
modular
synthesis
biologically
active
compounds
key
alcohol-containing
synthetic
intermediates.
Preliminary
mechanistic
studies
shed
light
on
neutral
coordination
functionality
to
nickel
catalyst
origin
regioselectivity.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(47), С. 32235 - 32242
Опубликована: Ноя. 13, 2024
The
direct
use
of
readily
available
aldehydes
as
acyl
radical
precursors
has
facilitated
diverse
three-component
acylative
difunctionalization
reactions
alkenes,
offering
a
powerful
route
to
synthesize
β-branched
ketones.
However,
asymmetric
alkenes
with
still
remains
elusive.
Here
we
report
copper-catalyzed
acylarylation
vinylarenes
and
aryl
boronic
acids.
This
method
begins
formation
from
an
aldehyde
via
hydrogen
atom
transfer.
adds
the
alkene,
forming
new
benzylic
that
then
undergoes
enantioselective
arylation.
A
chiral
binaphthyl-tethered
bisoxazoline
ligand
is
essential
for
achieving
high
stereocontrol.
strategy
enables
synthesis
range
synthetically
valuable
β,β-diaryl
ketones
vinylarenes.
