Comparison of Phosphonium and Sulfoxonium Ylides in Ru(II)-Catalyzed Dehydrogenative Annulations: A Density Functional Theory Study
Wei Zhou,
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Lei Zhang,
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Dan-Yang Liu
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et al.
Molecules,
Journal Year:
2025,
Volume and Issue:
30(9), P. 1883 - 1883
Published: April 23, 2025
Density
functional
theory
calculations
have
been
performed
to
explore
the
detailed
mechanism
of
a
ruthenium-catalyzed
dehydrogenative
annulation
between
α-carbonyl
phosphonium
ylide
(A)
and
sulfoxonium
(B).
The
proposed
catalytic
cycles
consist
several
elementary
steps
in
succession,
namely
C–H
activation
A,
insertion
B,
reductive
elimination,
protodemetallation,
an
intramolecular
Wittig
reaction,
which
is
rate-limiting,
with
free
energy
barrier
31.7
kcal/mol.
As
A
B
are
both
capable
being
substrate
carbene
precursor,
there
potentially
four
competing
pathways
including
homo-coupling
reactions.
Further
demonstrate
that
more
reactive
step
than
while
opposite
conclusion
true
for
step,
can
successfully
explain
fact
solely
observed
product
originated
from
use
as
precursor.
Molecular
electrostatic
potential,
charge
decomposition,
electron
density
difference
analyses
were
understand
distinct
behaviors
two
ylides
nature
key
ruthenium–carbene
intermediate.
Language: Английский
Iridium(III)-Catalyzed Cyclization of Oximes with Iodonium Ylides: Synthesis of Multisubstituted Heterocyclic N-Oxides
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 29, 2025
Iridium(III)-catalyzed
regioselective
cyclization
of
substituted
oximes
with
iodonium
ylides
has
been
described.
This
methodology
offered
multisubstituted
heterocyclic
N-oxides
under
mild
reaction
conditions
in
a
redox-neutral
manner.
The
was
also
compatible
vinyl
oximes.
Additionally,
substrate
diversification
carried
out
to
illustrate
the
synthetic
application
protocol.
A
possible
mechanism
involving
C-H
bond
activation
proposed
as
well
supported
by
isolation
key
five-membered
iridacycle
intermediate.
Language: Английский