The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(12), P. 8896 - 8905
Published: June 10, 2024
Endocyclic
1-azaallyl
anions
engage
allyl
acetates
in
a
palladium-catalyzed
allylation
followed
by
reduction
to
give
unprotected
2-(hetero)aryl-3-allylpiperidines
and
2-allyl-3-arylmorpholines,
products
not
easily
accessible
other
means.
The
group
is
then
readily
transformed
into
variety
of
functional
groups.
Preliminary
studies
on
the
asymmetric
variant
reaction
using
an
enantiomerically
pure
BI-DIME-type
ligand
provide
product
with
moderate
enantioselectivity.
Computational
suggest
that
energy
barriers
inner-sphere
reductive
elimination
outer-sphere
nucleophilic
substitution
are
almost
same,
which
makes
both
them
possible
pathways.
In
addition,
mechanism
displays
enantiodiscriminating
C–C
bond
forming
step,
while
much
less
selective,
combined
Advanced Synthesis & Catalysis,
Journal Year:
2022,
Volume and Issue:
365(6), P. 826 - 833
Published: Nov. 30, 2022
This
study
reports
the
synthesis
of
diverse
β-functionalized
ketones
from
readily
available
1-arylallylic
alcohols
in
presence
(trimethylsilyl)methylpotassium
(TMSCH2K).
The
reaction
proceeded
via
formation
highly
nucleophilic
dipotassio
α,β-dianion
as
key
intermediate,
which
served
a
metal
homoenolate
equivalent.
protocol
also
allowed
one-pot
α,β-difunctionalized
using
two
different
electrophiles,
thus
demonstrating
its
synthetic
advantages
over
other
protocols
involving
homoenolates.
As
service
to
our
authors
and
readers,
this
journal
provides
supporting
information
supplied
by
authors.
Such
materials
are
peer
reviewed
may
be
re-organized
for
online
delivery,
but
not
copy-edited
or
typeset.
Technical
support
issues
arising
(other
than
missing
files)
should
addressed
Please
note:
publisher
is
responsible
content
functionality
any
Any
queries
content)
directed
corresponding
author
article.
Organic Chemistry Frontiers,
Journal Year:
2022,
Volume and Issue:
10(2), P. 399 - 403
Published: Nov. 30, 2022
We
report
herein
a
concise
and
useful
method
for
the
construction
of
3-substituted
indole
derivatives
via
palladium-catalyzed
ring-opening
coupling
reaction
cyclopropanols
with
N
-allenyl-2-iodoanilines.
Advanced Science,
Journal Year:
2023,
Volume and Issue:
11(9)
Published: Dec. 21, 2023
Abstract
An
unprecedented
Et
2
Zn‐mediated
gem‐dicarboxylation
of
C─C/C─H
single
bond
cyclopropanols
with
CO
is
disclosed,
which
provides
a
straightforward
and
efficient
methodology
for
the
synthesis
variety
structurally
diverse
useful
malonic
acids
in
moderate
to
excellent
yields.
The
protocol
features
mild
reaction
conditions,
functional
group
compatibility,
broad
substrate
scope,
facile
derivatization
products.
DFT
calculations
confirm
that
transition‐metal‐free
transformation
proceeds
through
novel
ring‐opening/
α
‐functionalization/ring‐closing/ring‐opening/
β
‐functionalization
(ROFCOF)
process,
1,8‐diazabicyclo[5.4.0]undec‐7‐ene
(DBU)
plays
dual
important
roles
transformation.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(12), P. 8896 - 8905
Published: June 10, 2024
Endocyclic
1-azaallyl
anions
engage
allyl
acetates
in
a
palladium-catalyzed
allylation
followed
by
reduction
to
give
unprotected
2-(hetero)aryl-3-allylpiperidines
and
2-allyl-3-arylmorpholines,
products
not
easily
accessible
other
means.
The
group
is
then
readily
transformed
into
variety
of
functional
groups.
Preliminary
studies
on
the
asymmetric
variant
reaction
using
an
enantiomerically
pure
BI-DIME-type
ligand
provide
product
with
moderate
enantioselectivity.
Computational
suggest
that
energy
barriers
inner-sphere
reductive
elimination
outer-sphere
nucleophilic
substitution
are
almost
same,
which
makes
both
them
possible
pathways.
In
addition,
mechanism
displays
enantiodiscriminating
C–C
bond
forming
step,
while
much
less
selective,
combined
