Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 4, 2024
Comprehensive
Summary
Herein,
an
unprecedented
nickel‐catalyzed
regioselective
hydroalkynylation
of
unsymmetrical
internal
alkynes
was
realized
with
steric
hindered
resistance
selectivity
via
the
cyano‐directing
group
strategy.
Significantly,
resulting
1,3‐enyne
products
could
be
effectively
employed
in
synthesis
novel
nitrogen‐containing
tricyclics
compounds,
that
provided
potential
candidate
compound
8a
(IC
50
=
2.6—6.1
μmol/L)
for
anti‐tumor
cell
proliferation
activity.
Therefore,
this
work
not
only
improves
transition‐metal‐
catalyzed
strategy
alkynes,
but
also
exhibits
versatility
1,3‐enynes
construction
complex
bioactive
chemical
space.
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.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
147(2), С. 1667 - 1676
Опубликована: Янв. 7, 2025
We
report
a
Ni-catalyzed
vicinal
alkylarylation
of
unactivated
alkenes
in
γ,δ-
and
δ,ε-alkenylamines
with
aryl
halides
alkylzinc
reagents.
The
reaction
is
enabled
by
amine
coordination
can
use
all
primary,
secondary,
tertiary
amines.
constructs
two
new
C(sp3)-C(sp3)
C(sp3)-C(sp2)
bonds
produces
δ-
ε-arylamines
C(sp3)-branching
at
the
γ-
δ-positions.
A
variety
heteroaryl
iodides
both
primary
secondary
reagents
be
used
as
coupling
carbon
sources.
Mechanistic
studies
suggest
that
cooperative
effect
organic
nitriles
electron-deficient
(EDAs)
ligands.
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.
Chemical Science,
Год журнала:
2025,
Номер
16(10), С. 4442 - 4449
Опубликована: Янв. 1, 2025
Catalytic
methods
by
switching
the
least
parameters
for
regioselective
and
site-divergent
transformations
to
construct
different
architectures
from
identical
readily
available
starting
materials
are
among
most
ideal
catalytic
protocols.
However,
associated
challenge
precisely
control
both
regioselectivity
site
diversity
renders
this
strategy
appealing
yet
challenging.
Herein,
Ni-catalyzed
cross-electrophile
1,2-
1,3-arylalkylations
of
N-acyl
allylic
amines
have
been
developed.
This
reductive
three-component
protocol
enables
1,2-arylalkylation
1,3-arylalkylation
with
aryl
halides
alkyl
excellent
chemo-,
regio-
site-selectivity,
representing
first
example
controlled
migratory
difunctionalization
alkenes
under
conditions.
A
wide
range
terminal
internal
unactivated
amines,
precursors
were
tolerated,
providing
straightforward
efficient
access
diverse
C(sp3)-rich
branched
aliphatic
materials.
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.
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.
Chiral
alpha-amino
ketones
have
found
extensive
applications
as
functional
molecules.
A
nickel-catalyzed,
enantioselective,
and
fully
intermolecular
three-component
1,2-alkylacylation
of
N-acyl
enamides
has
been
realized
with
tertiary
alkyl
bromides
carboxylic
acid-derived
electrophiles
the
coupling
reagents.
This
reductive
strategy
is
operationally
simple,
exhibiting
broad
substrate
scope
excellent
group
tolerance
using
readily
available
starting
materials
allowing
rapid
access
to
structurally
complex
α-amino
ketone
derivatives
in
high
enantioselectivity.
suitable
chiral
biimidazoline
ligand
together
additional
chelation
amide
carbonyl
a
Ni
intermediate
facilitates
enantioselective
control
by
suppressing
background
reaction,
accounting
for
Mechanistic
studies
indicated
intermediacy
radical
species.
