The Journal of Organic Chemistry,
Journal Year:
2019,
Volume and Issue:
85(2), P. 1126 - 1137
Published: Dec. 6, 2019
Despite
recent
advances,
a
general
method
for
the
synthesis
of
α-carbonyl-α′-(hetero)aryl
sulfoxonium
ylides
is
needed
to
benefit
more
greatly
from
potential
safety
advantages
offered
by
these
compounds
over
parent
diazo
compounds.
Herein,
we
report
palladium-catalyzed
cross-coupling
aryl
bromides
and
triflates
with
α-carbonyl
ylides.
We
also
use
this
modification
an
active
pharmaceutical
ingredient
key
precursor
antagonists
neurokinin-1
receptor.
In
addition,
mechanism
reaction
was
inferred
several
observations.
Thus,
oxidative
addition
complex
[(XPhos)PhPdBr]
its
dimer
were
observed
31P{1H}
NMR,
complexes
shown
be
catalytically
kinetically
competent.
Moreover,
resulting
transmetalation
[(XPhos)ArPdBr]
(Ar
=
p-CF3–C6H4)
model
ylide
mass
spectrometry.
Finally,
partial
rate
law
suggests
that
subsequent
deprotonation
are
rate-determining
in
catalytic
cycle.
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
29(1)
Published: Oct. 17, 2022
Tuning
the
redox
potential
of
commonly
available
photocatalyst
to
improve
catalytic
performance
or
expand
its
scope
for
challenging
synthetic
conversions
is
an
ongoing
demand
in
chemistry.
Herein,
excited
state
properties
and
commercially
[Ru(bpy)3
]2+
were
tuned
by
modifying
structure
bipyridine
ligands
with
electron-donating/withdrawing
units.
The
visible-light-mediated
photoredox
phosphorylation
tertiary
aliphatic
amines
was
demonstrated
under
mild
conditions.
A
series
cross-dehydrogenative
coupling
reactions
performed
employing
RuII
complexes
as
giving
corresponding
α-aminophosphinoxides
α-aminophosphonates
via
carbon-phosphorus
(C-P)
bond
formation.
ChemCatChem,
Journal Year:
2023,
Volume and Issue:
15(7)
Published: Feb. 7, 2023
Abstract
The
study
of
the
reactivity
cyclic
sulfoxonium
ylides
has
been
so
far
neglected,
in
particular
for
reactions
that
forms
carbon‐carbon
bond
at
ylide
carbon
atom.
Herein,
we
describe
synthesis
by
palladium‐catalyzed
intramolecular
arylation
and
these
C3‐alkylation
indoles
presence
either
an
acid
catalyst
or
iridium
catalyst.
This
revealed
catalysis
is
only
efficient
which
tether
a
six‐membered
lactone,
whereas
was
better
suited
to
reaction
five‐membered
ring
ketone
lactone.
observed
chemospecificity
might
be
due
relative
basicity
under
steric
hindrance
around
carbene
intermediate
when
conducted
with
Advanced Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 2, 2025
Amide
and
alkene
moieties
are
frequently
found
in
natural
products
privileged
structures
pharmaceuticals
agrochemicals.
Moreover,
vinyl
sulfoxonium
ylide
can
be
converted
into
a
broad
range
of
high-value
compounds,
thus
they
have
been
widely
employed
organic
synthesis.
However,
the
synthesis
alkene-substituted
amide-sulfoxonium
ylides
via
intermolecular
hydrocarbonation
alkynes
remains
underexplored.
This
study
describes
development
high-throughput
approach
to
provide
diverse
functionalized
E-alkene
substituted
(hetero)amide-sulfoxonium
ylides.
The
reaction
occurs
under
mild
metal-free
conditions,
employing
as
highly
effective
nucleophiles,
which
participate
Michael
addition
reactions
with
various
alkynes,
such
esters,
thioesters,
ketones,
amides,
sulfones.
low-cost,
operationally
simple
has
substrate
scope,
high
functional
group
compatibility,
excellent
regio-
stereoselectivity,
making
it
suitable
for
transformation
structurally
complex
molecules.
Furthermore,
obtained
stabilized
directly
useful
valuable
1,5-dicarbonyl
thiabenzene
1-oxide
compounds.
The Journal of Organic Chemistry,
Journal Year:
2019,
Volume and Issue:
85(2), P. 1126 - 1137
Published: Dec. 6, 2019
Despite
recent
advances,
a
general
method
for
the
synthesis
of
α-carbonyl-α′-(hetero)aryl
sulfoxonium
ylides
is
needed
to
benefit
more
greatly
from
potential
safety
advantages
offered
by
these
compounds
over
parent
diazo
compounds.
Herein,
we
report
palladium-catalyzed
cross-coupling
aryl
bromides
and
triflates
with
α-carbonyl
ylides.
We
also
use
this
modification
an
active
pharmaceutical
ingredient
key
precursor
antagonists
neurokinin-1
receptor.
In
addition,
mechanism
reaction
was
inferred
several
observations.
Thus,
oxidative
addition
complex
[(XPhos)PhPdBr]
its
dimer
were
observed
31P{1H}
NMR,
complexes
shown
be
catalytically
kinetically
competent.
Moreover,
resulting
transmetalation
[(XPhos)ArPdBr]
(Ar
=
p-CF3–C6H4)
model
ylide
mass
spectrometry.
Finally,
partial
rate
law
suggests
that
subsequent
deprotonation
are
rate-determining
in
catalytic
cycle.
