Empowering Diastereoselective Cyclopropanation of Unactivated Alkenes with Sulfur Ylides through Nucleopalladation
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 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.
Language: Английский
Asymmetric cyclopropanation via electro-organocatalytic cascade
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Jan. 1, 2024
The
work
demonstrates
the
successful
merger
of
electrochemistry
with
asymmetric
iminium
ion
organocatalysis.
Language: Английский