Catalytic Dearomative [1,5]‐Sigmatropic Carbon Shift of Heterole‐Fused Norcaradienes Enabled Concise Helicenation
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 21, 2024
In
contrast
to
the
locked
fluxionality
of
norcaradienes
fused
by
benzene,
unexplored
less
aromatic
heterole-fused
norcaradienes,
creatively
generated
intramolecular
hydroarylation
heteroaryl
alkynylcyclopropanes,
reserve
a
balancing
that
permits
dearomative
[1,5]-sigmatropic
carbon
shift
akin
reduced
aromaticity
heterole.
This
"walk"
was
confirmed
isolation
cycloheptatriene
species
derived
from
ring-expansion
dearomatized
alkynylated
norcaradiene.
A
following
ester-directed
ring-opening
rearomatization
these
gives
products
featuring
migratory
acylmethyls
are
competent
for
helicenation
with
neighboring
(hetero)
arenes
via
(formal)
dehydrative
alkenylation.
Such
reactivity
will
open
up
opportunity
development
controllable
reactions
norcaradienes.
Language: Английский
Catalytic Dearomative [1,5]‐Sigmatropic Carbon Shift of Heterole‐Fused Norcaradienes Enabled Concise Helicenation
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 21, 2024
Abstract
In
contrast
to
the
locked
fluxionality
of
norcaradienes
fused
by
benzene,
unexplored
less
aromatic
heterole‐fused
norcaradienes,
creatively
generated
intramolecular
hydroarylation
heteroaryl
alkynylcyclopropanes,
reserve
a
balancing
that
permits
dearomative
[1,5]‐sigmatropic
carbon
shift
akin
reduced
aromaticity
heterole.
This
“walk”
was
confirmed
isolation
cycloheptatriene
species
derived
from
ring‐expansion
dearomatized
alkynylated
norcaradiene.
A
following
ester‐directed
ring‐opening
rearomatization
these
gives
products
featuring
migratory
acylmethyls
are
competent
for
helicenation
with
neighboring
(hetero)
arenes
via
(formal)
dehydrative
alkenylation.
Such
reactivity
will
open
up
opportunity
development
controllable
reactions
norcaradienes.
Language: Английский