Regioselective intermolecular carboamination of allylamines via nucleopalladation: empowering three-component synthesis of vicinal diamines
Chemical Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
Intermolecular
carboamination
of
allyl
amines
under
Pd(
ii
)-catalysis
is
reported,
expediting
the
synthesis
vicinal
diamines
embedded
in
a
functionally
enriched
linear
carbon
framework
with
high
yields
and
exclusive
Markovnikov
selectivity.
Язык: Английский
Ni-Catalyzed Regioselective and Site-divergent Reductive Arylalkylations of Allylic Amines
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.
Язык: Английский
Palladium(II)-Catalyzed Regioselective Hydroamination of Allylamines to N-Alkyl Sulfoximines
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 14, 2025
An
intermolecular
coupling
between
sulfoximines
and
allyl
amines,
linked
to
the
picolinamide
directing
group,
is
developed
by
leveraging
a
nucleopalladation-guided
regioselective
hydroamination
strategy,
enabling
production
of
range
valuable
N-alkyl
in
high
yields.
The
protocol
features
operational
simplicity
broad
substrate
scope
was
also
amenable
aniline
nucleophiles.
Synthetic
utilities
were
showcased
through
scale-up
reactions
product
diversifications,
leading
biorelevant
molecules.
Язык: Английский
Empowering Diastereoselective Cyclopropanation of Unactivated Alkenes with Sulfur Ylides through Nucleopalladation
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 7, 2025
Regio-
and
stereoselective
cyclopropanation
of
unactivated
alkenes
under
mild
conditions
remains
a
challenging
yet
fundamental
transformation.
We
present
versatile
palladium(II)-catalyzed
method
for
the
diastereoselective
alkenyl
amines
acids,
which
leverages
nucleopalladation
mechanism
unique
ambiphilic
reactivity
sulfur
ylides.
This
Pd(II)/Pd(IV)
catalytic
protocol
selectively
delivers
anti-cyclopropanes
allylamines
with
removable
isoquinoline-1-carboxamide
auxiliary,
while
enabling
excellent
syn-selectivity
acid
derivatives
containing
2-(aminomethyl)pyridine
derivative
as
directing
group.
The
is
operationally
simple
scalable,
features
wide
substrate
generality,
also
effective
in
presence
various
medicinally
relevant
scaffolds.
cyclopropane
products
were
further
transformed
into
1,2,3-trifunctionalized
cyclopropanes
engaged
an
aza-Piancatelli
reaction,
introducing
additional
molecular
complexity.
DFT
studies
performed
to
shed
light
on
reaction
origins
observed
stereoselectivity.
Язык: Английский
Dehydrogenative α,γ-Diphosphinylation of Allylamines Enabled by Photoinduced Cobaloxime Catalysis
Organic Letters,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 18, 2024
A
regioselective
radical
α,γ-diphosphinylation
of
allylamines
with
secondary
phosphine
oxides
by
photoinduced
cobaloxime
catalysis
is
described.
The
reaction
tolerates
a
wide
range
and
oxides,
affording
α-amino
diphosphine
dioxides
in
moderate
to
good
yields
hydrogen
evolution.
synthesis
new
monoxide
ligands
the
promising
antitumor
activities
products
demonstrate
great
potential
applications
this
approach
drug
discovery.
detailed
mechanism
studies
indicate
that
likely
proceeds
through
dehydrogenative
allylic
phosphinylation
nucleophilic
addition
process.
Язык: Английский