ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(24), P. 18841 - 18850
Published: Dec. 11, 2024
Herein,
we
present
a
practical
strategy
for
the
asymmetric
synthesis
of
chiral
acyclic
nitriles
featuring
α-all-carbon
quaternary
stereocenters,
utilizing
synergistic
palladium
and
phase-transfer
catalysis
from
allyl
2-cyanoacetates
under
mild
conditions.
This
approach
offers
an
efficient
reliable
method
in
situ
generation
tertiary
α-cyano
carbanions
through
intramolecular
palladium-catalyzed
decarboxylative
allylic
alkylation.
Additionally,
it
enables
highly
enantioselective
control
simple
via
ion-pairing
interactions
with
catalysts.
The
synthetic
utility
this
is
further
demonstrated
by
its
scalability
to
gram-scale
subsequent
transformation
into
variety
functionalized
compounds
containing
all-carbon
stereocenters.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(7), P. 5019 - 5028
Published: March 19, 2024
In
this
paper,
we
reported
the
palladium-catalyzed
formal
[5
+
4]
cycloaddition
reactions
between
4-vinyl-4-butyrolactones
(VBLs)
and
azadienes.
Under
mild
reaction
conditions,
a
wide
range
of
benzofuran-fused
9-membered
heterocyclic
compounds
had
been
provided
in
moderate
to
excellent
yields
with
exclusive
regioselectivities
diastereoselectivities.
The
practical
applicability
synthesis
was
demonstrated
through
scale-up
further
transformation.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(20)
Published: Jan. 29, 2024
To
facilitate
the
discovery
and
development
of
new
pharmaceuticals,
demand
for
novel
stereofunctionalised
building
blocks
has
never
been
greater.
Whilst
molecules
bearing
quaternary
tetrasubstituted
stereogenic
centres
are
ideally
suited
to
explore
untapped
areas
chemical
space,
asymmetric
construction
ofsterically
congested
carbon
remains
a
longstanding
challenge
in
organic
synthesis.
The
enantioselective
assembly
acyclic
is
even
more
demanding
due
need
restrict
much
wider
range
geometries
conformations
intermediates
involved.
In
this
context,
catalytic
allylicalkylation
(AAA)
prochiral
nucleophiles,
namely
enolates,
become
an
indispensable
tool
access
linearα-quaternary
andα-tetrasubstituted
carbonyl
compounds.
However,
unlike
AAA
cyclic
enolates
with
fixed
enolate
geometry,
achieve
high
levels
stereocontrol
stereoselectivity
enolisation
must
be
considered.
aim
review
offer
acomprehensivediscussion
reactions
their
analogues
generate
chiral
using
metal,
non-metal
dual
catalysis,
particular
focus
given
control
geometry
its
impact
on
stereochemical
outcome
reaction.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 10, 2025
A
palladium-catalyzed
decarboxylative
allylic
sulfonylation
reaction
of
vinyloxazolidine-2,4-diones
with
inexpensive
and
readily
available
sodium
sulfinates
as
reagents
has
been
developed.
Under
the
catalysis
Pd(PPh3)4,
a
wide
range
γ-sulfonyl-α,β-unsaturated
amides
can
be
synthesized
in
good
to
excellent
yields.
The
developed
protocol
is
characterized
by
exclusive
regioselectivity,
mild
conditions,
broad
substrate
scope,
functional
group
tolerance,
suitable
for
gram-scale
synthesis.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 2, 2025
Herein,
we
report
the
concise
total
syntheses
of
(+)-leucolusine
and
(-)-7-epi-leucolusine
achieved
in
8
steps
starting
from
commercially
available
piperidin-2-one.
Our
strategy
highlights
a
palladium-catalyzed
decarboxylative
asymmetric
allylic
alkylation
for
constructing
δ-lactam
bearing
C20
all-carbon
quaternary
stereocenter.
Additionally,
cis-fused
octahydrofuro[2,3-b]pyridine
unit
was
efficiently
constructed
via
one-pot
protocol
encompassing
reduction
oxa-Mannich-type
cyclization
processes.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(21)
Published: Feb. 7, 2024
Linearly
fused
polycyclic
piperidines
represent
common
substructures
in
natural
products
and
biologically
active
small
molecules.
We
have
devised
a
Pd-catalyzed
annulation
strategy
to
these
compounds
that
converts
readily
available
2-tetralones
indanones
into
scaffolds
with
the
potential
for
control
of
both
enantio-
diastereoselectivity.
Importantly,
can
be
chemoselectively
functionalized,
providing
an
efficient
robust
methodology
important
nitrogen-containing
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(15), P. 4131 - 4137
Published: Jan. 1, 2024
A
palladium-catalyzed
decarboxylative
(5
+
5)
cyclization
reaction
of
vinyloxazolidine-2,4-diones
for
the
synthesis
ten-membered
N,O-containing
heterocycles
is
disclosed.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(21), P. 4294 - 4322
Published: Aug. 17, 2024
Abstract
Optically
active
molecule
architectures
stand
as
an
important
class
of
organic
compounds
and
occupy
a
key
role
in
academic
industrial
communities.
Particularly,
the
molecules
bearing
quaternary
carbon
are
vital
importance
because
its
favorable
conformation
valuable
three‐dimensional
molecules,
which
frequently
play
broad
spectrum
functional
materials,
pharmaceutical
relevant
natural
agrochemicals.
Over
past
few
decades,
large
number
synthetic
strategies
for
enantioselective
construction
with
chiral
centers
have
been
focus
research
initiatives.
In
this
review,
state‐of‐the‐art
toward
synthesis
enantioenriched
stereocenters
summarized,
could
be
segmented
into
four
categories:
1)
Construction
optically
by
addition
to
prochiral
sp
2
carbon;
2)
all‐carbon
via
substitution
at
non‐chiral
tetra‐substituted
3)
kinetic
resolution;
4)
desymmetrization
reactions.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(12), P. 8363 - 8375
Published: June 7, 2024
Palladium-catalyzed
decarboxylation
of
5-methylene-1,3-oxazinan-2-ones
and
5-methylene-1,3-dioxan-2-ones
to
generate
aza-π-allylpalladium
oxa-π-allylpalladium
1,4-dipoles
for
[4
+
2]
cycloaddition
reaction
with
1,3,5-triazinanes
was
developed,
affording
a
wide
range
hexahydropyrimidine
1,3-oxazinane
derivatives
in
good
excellent
yields
(up
99%).
The
acyclic
sulfonamido-substituted
allylic
carbonates
as
1,4-dipole
precursors
also
apply
the
developed
synthesized
strategy,
achieving
synthesis
hexahydropyrimidines.
Moreover,
situ-generated
undergoing
dimeric
4]
were
demonstrated
by
construction
1,5-diazocane
derivatives.
