Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 23, 2024
Nickel-catalyzed
cross-electrophile
coupling
(XEC)
reactions
of
(hetero)aryl
electrophiles
represent
appealing
alternatives
to
palladium-catalyzed
methods
for
biaryl
synthesis,
but
they
often
generate
significant
quantities
homocoupling
and/or
proto-dehalogenation
side
products.
In
this
study,
an
informer
library
heteroaryl
chloride
and
aryl
bromide
partners
is
used
identify
Ni-catalyzed
XEC
conditions
that
access
high
selectivity
the
cross-product
when
using
equimolar
two
substrates.
Two
different
catalyst
systems
are
identified
show
complementary
scope
broad
functional-group
tolerance,
time-course
data
suggest
follow
mechanisms.
A
NiBr
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 31, 2024
We
report
herein
our
studies
on
the
direct
photoactivation
of
carbonyl
cyclopropanes
to
give
biradical
intermediates,
leading
selective
cleavage
more
substituted
carbon-carbon
bond.
Depending
substrate
structure,
extended
alkenes
were
isolated
or
directly
reacted
in
a
photo-Nazarov
process
bicyclic
products.
Based
these
results,
unified
reductive
ring-opening
reaction
was
developed
by
using
diphenyl
disulfide
as
hydrogen
atom
transfer
(HAT)
reagent.
By
performing
sequential
cyclopropanation/selective
ring
opening
reaction,
we
achieved
CH
Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 31, 2024
Abstract
We
report
herein
our
studies
on
the
direct
photoactivation
of
carbonyl
cyclopropanes
to
give
biradical
intermediates,
leading
selective
cleavage
more
substituted
carbon‐carbon
bond.
Depending
substrate
structure,
extended
alkenes
were
isolated
or
directly
reacted
in
a
photo‐Nazarov
process
bicyclic
products.
Based
these
results,
unified
reductive
ring‐opening
reaction
was
developed
by
using
diphenyl
disulfide
as
hydrogen
atom
transfer
(HAT)
reagent.
By
performing
sequential
cyclopropanation/selective
ring
opening
reaction,
we
achieved
CH
2
insertion
into
α,β
bond
both
acyclic
and
cyclic
unsaturated
compounds.
Our
protocol
provides
further
tool
for
modification
carbon
framework
organic
compounds,
complementing
recent
progress
“skeletal
editing”.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 23, 2024
Nickel-catalyzed
cross-electrophile
coupling
(XEC)
reactions
of
(hetero)aryl
electrophiles
represent
appealing
alternatives
to
palladium-catalyzed
methods
for
biaryl
synthesis,
but
they
often
generate
significant
quantities
homocoupling
and/or
proto-dehalogenation
side
products.
In
this
study,
an
informer
library
heteroaryl
chloride
and
aryl
bromide
partners
is
used
identify
Ni-catalyzed
XEC
conditions
that
access
high
selectivity
the
cross-product
when
using
equimolar
two
substrates.
Two
different
catalyst
systems
are
identified
show
complementary
scope
broad
functional-group
tolerance,
time-course
data
suggest
follow
mechanisms.
A
NiBr
