Palladium‐Catalyzed Dual Csp2─Csp3 Bond Formation: A Versatile Platform for the Synthesis of Benzo‐Fused Heterocycles
Advanced Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 28, 2025
Abstract
Transition‐metal‐catalyzed
transformations
offer
a
powerful
approach
to
rapidly
synthesize
complex
benzo‐fused
heterocycles,
crucial
for
drug
and
material
development.
However,
existing
synthetic
strategies
face
challenges
such
as
limited
functional
group
compatibility,
reliance
on
ligands,
difficulties
in
controlling
chemoselectivity
with
prefunctionalized
substrates.
Herein,
ligand‐free
Pd(II)/Cu(I)
catalytic
system
is
presented
that
facilitates
reactions
between
arylsulfonyl
chlorides
unactivated
olefins
under
mild
conditions,
enabling
the
efficient
synthesis
of
saturated
six‐membered
heterocycles.
This
streamlined
strategy
employs
dual
Csp
2
─Csp
3
bond
formation,
producing
diverse
N/O‐polyheterocycles
allowing
late‐stage
functionalization
bioactive
molecules
excellent
yields
high
chemoselectivity.
The
key
success
this
reaction
formation
high‐valent
Ar‐Pd(III)
intermediate,
which
drives
through
1,2‐Pd
migration
electrophilic
C─H
arylation.
unique
reactivity
pathway
heterocycles
while
effectively
avoiding
β‐H
elimination
typically
associated
Heck‐type
reactions.
Язык: Английский
Pd(II)/Cu(I) Co-catalyzed Dual C–H Functionalization of Indoles at C2 and C3 Positions Using Bifunctional Arylsulfonyl Reagents
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 20, 2025
A
Pd(II)/Cu(I)
co-catalyzed
dual
C-H
functionalization
strategy
enables
the
one-pot
synthesis
of
C2/C3-difunctionalized
indoles
using
arylsulfonyl
reagents.
In
this
method,
Cu(I)
reduces
S(VI)
reagents
to
generate
radicals,
which
react
with
Pd(II)
form
electrophilic
Ar-Pd(III)
intermediates.
These
intermediates
regioselectively
arylate
at
C2
position,
followed
by
Cu(II)-mediated
C3
deliver
final
products.
This
synergistic
method
enhances
efficiency,
waste,
and
streamlines
complex
indole
functionalization.
Язык: Английский