Remote Functionalization by Pd-Catalyzed Isomerization of Alkynyl Alcohols
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(27), С. 18606 - 18615
Опубликована: Июнь 28, 2024
In
recent
years,
progress
has
been
made
in
the
development
of
catalytic
methods
that
allow
remote
functionalizations
based
on
alkene
isomerization.
contrast,
protocols
alkyne
isomerization
are
comparatively
rare.
Herein,
we
report
a
general
Pd-catalyzed
long-range
alkynyl
alcohols.
Starting
from
aryl-,
heteroaryl-,
or
alkyl-substituted
precursors,
optimized
system
provides
access
preferentially
to
thermodynamically
more
stable
α,β-unsaturated
aldehydes
and
is
compatible
with
potentially
sensitive
functional
groups.
We
showed
migration
both
π-components
carbon–carbon
triple
bond
can
be
sustained
over
several
methylene
units.
Computational
investigations
served
shed
light
key
elementary
steps
responsible
for
reactivity
selectivity.
These
include
an
unorthodox
phosphine-assisted
deprotonation
rather
than
conventional
β-hydride
elimination
final
tautomerization
event.
Язык: Английский
Enantioselective Cobalt-Catalyzed Remote Hydroboration of Alkenylboronates
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 14, 2025
Heteroatomic
groups
in
alkenes
typically
direct
thermodynamically
favored
chain
walking
of
C═C
bonds
toward
themselves,
thereby
facilitating
C-H
bond
functionalization
near
the
heteroatoms.
We
present
herein
an
efficient
cobalt-catalyzed
contra-thermodynamic
remote
hydroboration
alkenylboronates
with
pinacolborane
to
synthesize
chiral
1,n-diboronates.
This
protocol
features
a
broad
substrate
scope,
high
functional
group
tolerance,
and
excellent
enantioselectivity.
Mechanistic
studies
indicate
involvement
chain-walking
process.
Gram-scale
reactions
various
product
derivatizations
further
highlight
its
practicality.
Язык: Английский