A Divergent Synthesis of Spiroindenes via Ligand‐Controlled [3+2]/[4+2] Cycloadditions of Zwitterionic π‐Propargyl Palladium Species with Benzofulvenes
Yong-Jie Long,
Xian-Hua Zhong,
Min Shi
и другие.
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 5, 2025
Comprehensive
Summary
A
divergent
synthesis
of
spiroindenes
through
a
palladium
catalyzed
cycloaddition
between
zwitterionic
π‐propargyl
species
and
benzofulvenes
in
moderate
to
good
yields
has
been
disclosed
along
with
functional
group
compatibility
broad
substrate
universality.
This
protocol
features
highly
regioselective
switchable
process
[3+2]
[4+2]
cycloadditions
controlled
by
phosphine
ligands
different
bite
angles.
The
reaction
mechanism
clarified
mechanistic
studies
DFT
calculations,
rendering
that
the
coordination
modes
substrates
angle
play
critical
roles
product
regioselectivity.
Язык: Английский
Controlled chain-growth polymerization via propargyl/allenyl palladium intermediates
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Март 13, 2025
In
contrast
to
allyl
palladium
complexes,
propargylic/allenylic
species
display
complex
reactivities
that
limit
their
implementation
in
polymer
chemistry,
especially
for
chain-growth
polymerizations.
Here
we
report
an
example
of
controlled
polymerization
via
propargyl/allenyl
intermediates.
Vinylidenecyclopropane
1,1-dicarboxylate
(VDCP),
a
unique
allenylic
electrophile,
selectively
reacts
the
σ-allenyl
rather
than
more
common
π-propargyl
pathway,
thereby
unlocking
process.
Based
on
this
concept,
precise
synthesis
alkyne-backbone
polymers
is
realized,
featuring
fast
rate,
high
molecular
weight,
narrow
dispersity,
chemoselectivity,
and
excellent
end-group
fidelity.
We
demonstrate
preparation
unsaturated
macromolecules
with
advanced
sequences
architectures
using
method,
including
block,
gradient,
graft
copolymers.
chemistry.
Here,
authors
Язык: Английский
“Cesium Effect”-Mediated/Controlled Divergent Synthesis via Synergistic Pd/Cu-Catalyzed Cascade Reactions
Xian-Hua Zhong,
Yong-Jie Long,
Yin Wei
и другие.
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 8390 - 8402
Опубликована: Май 5, 2025
Язык: Английский
Mechanistic Investigation of the Pseudo-Halogen Effect in Enantioselective Aminocatalyzed [6 + 4] and [10 + 6] Cycloadditions: Enabling Unique Favorskii-Like Rearrangements
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 28, 2024
A
mechanistic
investigation
into
the
novel
combination
of
Язык: Английский
Theoretical Studies on the Reaction Mechanism for the Cycloaddition of Zwitterionic π-Allenyl Palladium Species: Substrate-Controlled Isomerization
Molecules,
Год журнала:
2024,
Номер
30(1), С. 103 - 103
Опубликована: Дек. 30, 2024
Zwitterionic
π-allenyl
palladium
species
are
newly
developed
intermediates.
A
substrate-controlled
step
existed
in
the
cycloaddition
of
zwitterionic
with
tropsulfimides
or
tropones.
With
assistance
previously
experimental
studies,
allenyl/propargyl
was
provenly
found
by
HRMS.
Further
DFT
calculation
studies
show
that
generated
through
oxidative
addition
Pd(0),
which
can
be
promoted
Lewis
acid
like
Yb(OTf)3,
and
more
likely
undergoes
an
outer
sphere
nucleophilic
attack.
The
isomerization
is
caused
difference
dissociation
energy
between
intermediation
tropones,
forming
specificity.
Язык: Английский