Enantioselective Synthesis of 1-Dihydrobenzazepines through Rh2(II)-Catalyzed Cycloisomerization of 1,6-Enyne
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 13, 2025
The
1-dihydrobenzazepine
skeleton
has
emerged
as
a
privileged
structural
motif
in
bioactive
molecules.
However,
due
to
lack
of
asymmetric
methodology,
access
chiral
1-dihydrobenzazepines
remained
limited.
Herein,
we
report
the
first
intermolecular
cycloisomerization
benzo-fused
enynes
for
synthesis
via
dirhodium
catalysis.
This
methodology
features
high
efficiency
(up
98%
yield),
enantioselectivity
99%
ee),
and
broad
scope
nucleophiles,
including
oxygen
nucleophiles
(alcohols,
phenols,
carboxylic
acids)
carbon
(silyl
enol
ethers).
Theoretical
experimental
mechanistic
studies
reveal
that
reaction
pathway
encompasses
an
cycloisomerization,
which
gives
rise
carbene
containing
donor–acceptor
(D-A)
cyclopropane
moiety,
followed
by
ring-opening
process
stereoselective
nucleophilic
attack
external
on
cyclopropyl
ring.
Control
experiments
demonstrate
pivotal
role
terminal
group
capped
alkynyl
substrates
achieving
good
efficiency.
Язык: Английский
Copper-Catalyzed Asymmetric Cloke–Wilson Rearrangement
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 7, 2025
Herein
we
describe
the
first
transition-metal-catalyzed
asymmetric
Cloke-Wilson
rearrangement
through
unprecedented
propargylic
alkenoxylation
reaction
with
enol
as
O-nucleophile.
A
set
of
new
chiral
PPBOX
ligands
was
prepared
to
guarantee
high
enantioselectivity
transformation.
series
polysubstituted
dihydrofuran
skeletons
bearing
an
alkyne
unit
in
good
yield
and
under
very
mild
conditions,
various
downstream
transformations
were
facilely
conducted
access
different
skeletons.
Язык: Английский