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.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Фев. 4, 2025
Asymmetric
multicomponent
reactions
that
aim
to
control
multiple
chiral
centers
with
high
selectivity
in
a
single
step
remain
an
on-gonging
challenge.
The
realm
of
enantioselective
radical-polar
crossover
transformation
achieved
through
C-H
Functionalization
has
yet
be
fully
explored.
Herein,
we
present
successful
description
photoredox/Cr-catalyzed
three-component
(hetero)arylalkylation
1,3-dienes
functionalization.
A
diverse
array
homoallylic
alcohols
could
obtained
good
excellent
yields,
accompanied
by
outstanding
enantioselectivity.
asymmetric
build
two
simultaneously
and
demonstrates
broad
substrate
tolerance,
accommodating
various
drug-derived
aldehydes,
(hetero)aromatics,
1,3-diene
derivatives.
Preliminary
mechanistic
studies
indicate
the
involvement
radical
intermediate,
allylic
chromium
species
reacting
aliphatic
aromatic
aldehydes
Zimmerman–Traxler
transition
states
enabled
dual
photoredox
catalysis.
ongoing
Here,
authors
photoredox-
chromium-catalyzed
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 4395 - 4406
Опубликована: Март 8, 2024
Asymmetric
reductive
three-component
arylalkylation
of
alkenes
via
the
radical
relay
method
has
been
well
established,
while
asymmetric
migratory
insertion
strategy
remains
unexplored.
We
report
enantioselective
nickel-catalyzed
cross-electrophile
with
aryl-
and
alkyl
halides
an
integrated
Heck
carbometalation/radical
cross-coupling
sequence.
This
protocol
employing
a
chiral
Ni/PHOX
catalytic
system
allows
terminal
internal
to
successfully
engage
exquisite
control
regio-,
chemo-,
stereoselectivity.
More
importantly,
this
undergoes
regio-
arylnickelation
followed
by
Csp3–Csp3
elimination,
thus
exhibiting
reverse
regioselectivity
method.
Mild
reaction
conditions
exceptional
functional
group
tolerance
facilitate
method's
compatibility
bioactive
motifs
modular
synthesis
biologically
active
compounds.
The
experiments
density
theory
calculations
provide
insights
into
mechanism
origin
stereoselectivity,
hemilabile
nature
PHOX
ligand
is
critical
for
achieving
arylalkylation.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(24), С. 16892 - 16901
Опубликована: Июнь 6, 2024
The
development
of
a
catalytic
method
for
stereogenic
carbon
center
formation
holds
immense
significance
in
organic
synthesis.
Transition-metal-catalyzed
cross-coupling
reaction
has
been
regarded
as
straightforward
and
efficient
tool
stereoselectively
forging
C–C
bond.
Nevertheless,
the
creation
acyclic
all-carbon
quaternary-containing
vicinal
stereocenters
remains
notoriously
challenging
within
domain
chemistry
despite
their
prominence
various
bioactive
small
molecules.
Herein,
we
describe
palladium-catalyzed
asymmetric
multicomponent
trisubstituted
alkene
with
aryl
diazonium
salts
arylboronic
acids
to
realize
tertiary-quaternary
centers
high
regio-,
distereo-,
enantioselectivity.
Specifically,
precise
manipulation
stereoconfiguration
alkenes
enables
divergent
stereoselective
reaction,
thus
allowing
facile
construction
all
four
enantiomers.
Harnessing
ligand-swap
strategy
involving
chiral
bisoxazoline
an
achiral
fumarate
individually
accelerates
enantioselective
migratory
insertion
reductive
elimination
step
process,
supported
by
density
functional
theory
(DFT)
calculations,
obviating
requirement
neighboring
directing
group
internal
olefin
skeleton.
ACS Catalysis,
Год журнала:
2024,
Номер
14(20), С. 15790 - 15798
Опубликована: Окт. 10, 2024
Here,
we
report
a
photoredox
and
nickel-catalyzed
cross-electrophile
coupling
strategy
for
the
asymmetric
three-component
1,2-alkylarylation
of
vinyl
boronates
with
(hetero)aryl
bromides
(2°,
3°)-alkyl
redox-active
esters
in
presence
Hantzsch
ester.
With
fluorinated
pyridyl-substituted
chiral
biimidazoline
ligand,
this
reaction
enables
straightforward
access
to
wide
variety
synthetically
valuable
α-aryl
from
readily
available
starting
materials.
This
features
mild
conditions,
broad
substrate
generality,
good
functional
group
tolerance
proceeds
without
using
metal
reductants
or
alkyl
halides.
Furthermore,
alkenyl
halides
other
electron-deficient
alkenes
such
as
acrylates
phosphonates
can
be
applied
successfully.
Preliminary
mechanistic
studies
shed
light
on
potential
pathways
roles
organic
amines.
Chemical Science,
Год журнала:
2024,
Номер
15(24), С. 9353 - 9360
Опубликована: Янв. 1, 2024
An
expedient
synthesis
of
electron-deficient
styrenes
is
accomplished
through
decarboxylation
and
oxidation
via
halogen
ion
transfer.
The
resulting
umpoled
intermediates
undergo
a
rebound
elimination
to
furnish
olefins.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(67)
Опубликована: Авг. 13, 2024
Abstract
Difunctionalizations
of
alkenes
represent
one
the
most
straightforward
protocols
to
build
molecular
complexity
due
simultaneous
construction
two
vicinal
bonds
cross
π‐bond
alkenes.
It
is
extremely
attractive
yet
challenging
control
stereochemistry
outcome
this
event.
Over
past
years,
visible‐light
and
Ni‐catalyzed
asymmetric
difunctionalizations
provide
an
environmental
benign
promising
solution
for
saturated
carbon
centers
with
regio‐
enantioselectivity.
In
Concept,
initiative
progress
enantioselective
enabled
by
nickel
catalysis
has
been
summarized.
Moreover,
further
efforts
directions
development
mediated
discussed.
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.
ACS Catalysis,
Год журнала:
2025,
Номер
15(3), С. 1693 - 1703
Опубликована: Янв. 16, 2025
The
enantioselective
three-component
dicarbonfunctionalization
of
electronically
unactivated
alkenes
continues
to
pose
a
significant
challenge.
In
this
work,
copper-catalyzed
highly
regio-
and
fluoroalkylalkynylation
with
diverse
terminal
alkynes
fluoroalkyl
halides
under
mild
conditions
is
developed.
addition
halides,
Togni's
reagent
can
also
participate
in
the
reaction,
delivering
chiral
β-trifluoromethyl
high
enantioselectivities.
This
method
exhibits
good
functional
group
tolerance,
facilitating
late-stage
derivatization
variety
biologically
active
molecules.
success
chemistry
was
achieved
by
using
bulky
indene-substituted
BOPA
ligand.
DFT
calculations
indicate
that
radical
through
fluorine-directed
outer-sphere
pathway.
Mechanistic
studies
reveal
amide
crucial
for
achieving
stereoselectivities
because
exclusive
F···H
hydrogen
bonding
between
Mes
on
be
formed
stabilize
Si-radical
coupling
transition
state.
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.
