Cell Reports Physical Science,
Год журнала:
2022,
Номер
3(3), С. 100776 - 100776
Опубликована: Фев. 16, 2022
The
formation
of
thermodynamically
accessible
metallacycle
is
crucial
to
achieve
site-selective
C–H
bond
activation.
Here,
we
report
an
isocyanide-bridging
activation
through
the
a
five-membered
palladacycle.
As
such,
proximal
in
aldehyde
moiety
activated
selectively.
subsequent
palladium
shift
and
intramolecular
C=N
insertion
construct
valuable
isoindolinone
framework.
Compared
with
conventional
isocyanide-promoted
activation,
both
carbon
nitrogen
atoms
isocyanide
are
engaged
new
formations.
Notably,
three
types
isoindolinones
can
be
obtained
selectively
by
variations
reaction
conditions.
Mechanistic
studies
shed
light
on
pathways.
Moreover,
synthetic
potential
current
methodology
demonstrated
providing
concise
routes
key
intermediates
indoprofen,
indobufen,
aristolactams,
lennoxamine,
falipamil.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(28), С. 18811 - 18816
Опубликована: Июль 5, 2024
1,4-Palladium
migration
has
been
widely
used
for
the
functionalization
of
remote
C–H
bonds.
However,
this
mechanism
limited
to
aryl
halide
precursors.
This
work
reports
an
unprecedented
Pd0-catalyzed
cyclobutanation
protocol
producing
valuable
fused
cyclobutanes
starting
from
cycloalkenyl
(pseudo)halides.
reaction
takes
place
via
alkenyl-to-alkyl
1,4-Pd
migration,
followed
by
intramolecular
Heck
coupling.
The
method
performs
best
with
cyclohexenyl
precursors,
giving
access
a
variety
substituted
bicyclo[4,2,0]octenes.
Reactants
containing
N-methyl
or
methoxy
group
give
rise
azetidines
oxetanes,
respectively,
same
mechanism.
Kinetic
and
deuterium-labeling
studies
point
rate-limiting
C(sp3)–H
activation
step.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Май 20, 2025
Cephalotane
diterpenoids,
featuring
unique
and
complicated
carbon
skeletons
remarkable
antitumor
activities
from
the
Cephalotaxus
genus,
have
been
gaining
increasing
attention.
Herein,
we
report
asymmetric
divergent
total
synthesis
of
benzenoid
cephalotane-type
diterpenoids
containing
identical
6/6/6/5
tetracyclic
bridged
δ-lactone
skeleton
with
different
oxidation
states.
A
cascade
C(sp2)
C(sp3)-H
activation
has
developed
to
efficiently
prepare
characteristic
synthetically
challenging
through
a
pivotal
palladium/NBE-cocatalyzed
process.
The
feature
this
strategy
is
construction
three
C-C
bonds
(two
C(sp2)-C(sp3)
one
C(sp3)-C(sp3)
bond)
formation
two
cycles
chiral
centers
in
single
step.
application
method
for
rapid
assembly
demonstrated
concise
cephanolides
A-D
(1-4)
ceforalide
B
(5)
via
late-stage
modification.
Organic Letters,
Год журнала:
2022,
Номер
24(21), С. 3781 - 3785
Опубликована: Май 20, 2022
1,4-Palladium
migration
has
emerged
as
a
reliable
method
for
directed
C–H
functionalization.
In
contrast
to
coupling
with
carbon
nucleophiles,
limited
examples
heteroatom
nucleophiles
have
been
reported.
Herein
we
report
palladium-catalyzed
intermolecular
C(sp3)–H
phosphorylation
reaction
via
1,4-palladium
migration,
which
is
often
difficult
because
of
the
strong
coordination
phosphorus
reagents
palladium
catalysts.
Phosphorylation
bonds
accomplished
in
good
yields
excellent
regioselectivity.
The
judicious
selection
phosphine
ligand
proved
be
key
success
this
cascade
process.
Cell Reports Physical Science,
Год журнала:
2022,
Номер
3(3), С. 100776 - 100776
Опубликована: Фев. 16, 2022
The
formation
of
thermodynamically
accessible
metallacycle
is
crucial
to
achieve
site-selective
C–H
bond
activation.
Here,
we
report
an
isocyanide-bridging
activation
through
the
a
five-membered
palladacycle.
As
such,
proximal
in
aldehyde
moiety
activated
selectively.
subsequent
palladium
shift
and
intramolecular
C=N
insertion
construct
valuable
isoindolinone
framework.
Compared
with
conventional
isocyanide-promoted
activation,
both
carbon
nitrogen
atoms
isocyanide
are
engaged
new
formations.
Notably,
three
types
isoindolinones
can
be
obtained
selectively
by
variations
reaction
conditions.
Mechanistic
studies
shed
light
on
pathways.
Moreover,
synthetic
potential
current
methodology
demonstrated
providing
concise
routes
key
intermediates
indoprofen,
indobufen,
aristolactams,
lennoxamine,
falipamil.
