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.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(40), С. 8162 - 8169
Опубликована: Янв. 1, 2023
The
zwitterionic
π-allylpalladium
species,
also
known
as
dipoles,
are
important
synthons
widely
used
in
various
reactions
including
cycloaddition
and
allylic
substitution.
This
study
reported
the
development
of
a
new
indole-fused
precursor
compound
its
application
[4
+
2]
substitution
reactions.
As
result,
synthesis
pyrrolo[3,2,1-ij]quinazolin-3-one
7-vinyl
indole
compounds
was
achieved
with
moderate
to
good
yields.
Notably,
reaction
exhibited
excellent
regio-
stereoselectivity.
Molecules,
Год журнала:
2024,
Номер
29(6), С. 1202 - 1202
Опубликована: Март 7, 2024
A
practical
metal-free
and
additive-free
approach
for
the
synthesis
of
6/7/8-membered
oxacyclic
ketone-fused
isoxazoles/isoxazolines
tetracyclic
or
tricyclic
structures
is
reported
through
Csp3–H
bond
radical
nitrile
oxidation
intramolecular
cycloaddition
alkenyl/alkynyl-substituted
aryl
methyl
ketones.
This
convenient
enables
simultaneous
formation
isoxazole/isoxazoline
ketones
to
form
polycyclic
architectures
by
using
tert-butyl
nitrite
(TBN)
as
a
non-metallic
initiator
N–O
fragment
donor.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(15), С. 4131 - 4137
Опубликована: Янв. 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.
A
unique
catalyst-controlled
chemodivergent
strategy
to
access
2-vinyl
indolines
and
indole-2-acetates
by
overcoming
the
usual
allylic
reactivity
of
vinyl
ethylene
carbonates
(VECs)
via
a
tandem
C-H/C-O
bond
activation
sequence
is
disclosed
herein.
This
methodology
provides
useful
molecular
scaffolds
following
two
distinct
pathways
in
highly
step-
atom-economical
manner.
The
pathway
features
challenging
beta-hydroxide
elimination
Rh-catalyzed
transformation,
we
have
observed
unusual
competing
such
as
an
oxidative
insertion
MeOH
into
Rh(III)
give
putative
Rh(V)-H
intermediate.
Mechanistic
insights
unveil
new
mode
open
avenue
for
divergent
catalysis.
Post
synthetic
modification
annulated
products
add
additional
advantage
methodology.
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.
