Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(12), P. 2030 - 2035
Published: March 20, 2023
Ten-membered
lactones
are
the
core
units
of
many
biologically
active
natural
products
but
with
a
great
synthetic
challenge.
Based
on
principle
vinylogy,
novel
types
cyclic
vinylogous
anhydrides
have
been
designed
as
five-carbon
carbonyl
synthons,
further
applied
in
[5
+
5]
annulation
vinylethylene
carbonates
under
chiral
palladium
catalysis.
This
strategy
features
excellent
regioselectivity,
mild
conditions,
and
broad
substrate
scope,
affording
range
spiro
ten-membered
bearing
oxindole
pyrrolidinone
motif
yield
(up
to
99%)
moderate
high
enantioselectivity
89%
ee).
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.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 5796 - 5805
Published: March 25, 2025
The
transition
metal-catalyzed
asymmetric
[n
+
2]
cycloaddition
reaction
with
oxy-substituted
ketene
intermediates
remains
a
synthetic
challenge
due
to
the
limited
availability
of
suitable
precursors.
Herein,
we
report
visible-light-driven,
palladium-catalyzed
[4
vinyl
benzoxazinanones
siloxyketene
intermediates,
generating
structurally
diverse
chiral
quinolinone
derivatives
satisfactory
diastereo-
and
enantioselectivities.
transient
generation
siloxyketenes
from
α-ketoacylsilylanes
through
visible-light-induced
Brook
rearrangement
is
important
for
success
present
cycloaddition.
13C-labeling
experiments
reveal
pathway
involving
[1,3]-silyl
migration
process.
side
arm
effects
BOX
ligand
silyl
steric
hindrance
α-ketoacylsilanes
play
crucial
roles
in
stereoselectivity
control,
theoretical
calculations
provide
insights
into
stereochemical
outcome
reaction.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(23), P. 5971 - 5977
Published: Jan. 1, 2023
A
palladium-catalyzed
enantioselective
decarboxylative
allylic
alkylation
of
α-benzyl
cyanoacetates
with
methylene
cyclic
carbamates
was
developed
for
the
construction
nitrile-containing
acyclic
quaternary
carbon
stereocenters
good
results.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(12), P. 2030 - 2035
Published: March 20, 2023
Ten-membered
lactones
are
the
core
units
of
many
biologically
active
natural
products
but
with
a
great
synthetic
challenge.
Based
on
principle
vinylogy,
novel
types
cyclic
vinylogous
anhydrides
have
been
designed
as
five-carbon
carbonyl
synthons,
further
applied
in
[5
+
5]
annulation
vinylethylene
carbonates
under
chiral
palladium
catalysis.
This
strategy
features
excellent
regioselectivity,
mild
conditions,
and
broad
substrate
scope,
affording
range
spiro
ten-membered
bearing
oxindole
pyrrolidinone
motif
yield
(up
to
99%)
moderate
high
enantioselectivity
89%
ee).
