The Journal of Organic Chemistry,
Год журнала:
2019,
Номер
85(2), С. 1126 - 1137
Опубликована: Дек. 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.
Organic Letters,
Год журнала:
2024,
Номер
26(27), С. 5811 - 5816
Опубликована: Июнь 28, 2024
A
practical
strategy
for
the
construction
of
diverse
phosphonyl
and
thiofunctionalized
sulfoxonium
ylides
via
controllable
monofunctionalization
hybrid
I(III)/S(VI)
is
presented.
This
process
allows
efficient
P–H
insertion
under
Cu
catalysis,
enabling
synthesis
ylides,
whereas
reaction
with
sulfur-containing
reagents
including
AgSCF3,
KSC(S)OR,
KSCN
mild
conditions
resulted
in
α-trifluoromethylthiolation,
dithiocarbanation,
thiocyanation
accordingly.
Of
note,
wide
substrate
compatibility
(108
examples),
excellent
efficiency
(up
to
99%
yield),
gram-scale
experiments,
various
product
derivatizations
highlight
synthetic
utility
this
protocol.
Chinese Journal of Chemistry,
Год журнала:
2021,
Номер
39(6), С. 1646 - 1650
Опубликована: Фев. 26, 2021
Main
observation
and
conclusion
A
visible
light‐promoted
reaction
of
donor/acceptor
diazoalkanes
with
sulfoxides
towards
the
synthesis
synthetically
useful
sulfoxonium
ylides
was
reported.
The
occurred
under
sole
light
irradiation
without
need
any
transition‐metals
or
additives,
affording
corresponding
in
moderate
to
good
yields.
success
late‐stage
modification
natural
isolates
drug
candidates,
scale‐up
transformation
other
molecules
further
rendered
approach
valuable.
Organic Letters,
Год журнала:
2022,
Номер
24(35), С. 6386 - 6390
Опубликована: Авг. 26, 2022
A
novel
visible-light-promoted
coupling
of
diazoketones
with
sulfoxonium
ylides,
employing
a
violet
light-emitting
diode,
is
described
under
both
batch
and
continuous
flow
conditions.
This
transformation
permits
the
direct
synthesis
synthetically
useful
1,3-dicarbonyl
ylides
(33
examples,
21-85%
yields),
by
means
an
acylation
from
in
situ
selective
generation
ketenes.
The
reaction
performed
conditions
proved
to
be
very
efficient,
providing
higher
yields
shorter
times.
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Ноя. 3, 2022
The
development
of
novel
methodologies
for
the
introduction
sulfoxonium
group
under
mild
conditions
is
appealing
but
remains
underexplored.
Herein
we
report
synthesis
a
class
hypervalent
iodine
reagents
with
transferrable
group.
These
compounds
enable
mixed
iodonium-sulfoxonium
ylide
reactivity.
well-defined
are
examined
in
visible-light-promoted
cyclization
reactions
wide
range
unsaturated
bonds
including
alkenes,
alkynes,
nitriles,
and
allenes.
Two
distinct
pathways
identified,
which
controlled
by
substituent
bond.
cycloaddition
protocol
features
simple
operation,
reaction
conditions,
excellent
functional
tolerance,
affording
broad
sulfoxonium-containing
cyclic
structures
moderate
to
yields.
Furthermore,
sufoxonium
product
can
be
transformed
into
diverse
groups
structural
motifs
via
single
electron
transfer
transition-metal
catalysis.
Journal of Heterocyclic Chemistry,
Год журнала:
2023,
Номер
61(1), С. 29 - 70
Опубликована: Окт. 26, 2023
Abstract
Sulfur
ylides
are
versatile
structures
that
display
various
characteristics
and
participate
in
a
myriad
of
reactions
to
produce
simple,
effective,
sometimes
stereoselective
toward
synthesizing
sulfur‐containing
compounds.
Nonetheless,
their
fulfillment
tremendous
developments
have
been
made
this
field
the
past
few
decades.
In
comprehensive
review,
luminosity
is
illuminated
on
application
sulfur
involved
domino,
cascade
annulation
reactions,
carbene
trapping
reagents
with
chameleonic
reactivity.
numerous
decennary,
chemists
used
solvent‐dependent,
rhodium
catalyzed,
dealkylative
intercepted,
photochemical
reaction,
halotrifluoromethylation,
benzannulation,
amidation
name
such
as
Mizoroki–Heck,
Suzuki–Miyaura,
Sommelet–Hauser
rearrangements.
Moreover,
other
prime
applications
include
metal
catalysis,
epoxidation
carbonyl
compounds,
acylmethylation,
cyclomerization,
oxidation,
insertion
reactions.
Additionally,
some
extremely
useful
play
major
role
synthesis
medicinally
active
heterocycles
structural
motifs.
This
review
article
discusses
all
these
proposed
mechanisms,
current
scenario,
at
length.
tutorial
concludes
by
providing
future
outlook
investigation
into
compounds
synthesized
using
it
great
potential
be
industries,
laboratories,
pharmaceutical
companies,
drug
production,
clinical
use,
medicinal
chemistry,
agrochemical
purposes.
Current Organic Chemistry,
Год журнала:
2024,
Номер
28(13), С. 978 - 990
Опубликована: Май 6, 2024
Abstract:
Photochemical
reactions
offer
unparalleled
opportunities
to
access
elusive
chemical
pathways
and
develop
innovative
strategies
for
constructing
complex
molecules.
Within
organic
synthesis,
photochemical
have
become
indispensable
tools
accessing
molecular
structures,
such
as
pharmaceuticals
natural
products.
The
ability
of
sulfur
ylides
participate
in
these
diverse
processes
has
made
them
the
synthetic
chemist's
toolbox.
use
transformations
garnered
significant
attention
chemistry
community,
they
serve
powerful
intermediates
several
transformations.
This
review
article
presents
a
comprehensive
overview
mediated
by
ylides.
Herein,
we
describe
key
aspects
reactivity
presence
light.
compounds
can
be
classified
into
three
categories:
energy
acceptors,
electron
donors,
trapping
reagents.
Organic Letters,
Год журнала:
2021,
Номер
23(12), С. 4818 - 4822
Опубликована: Июнь 7, 2021
The
direct
synthesis
of
sulfoxonium
ylides
from
amides
by
selective
N–C(O)
cleavage
is
presented.
reaction
proceeds
through
the
nucleophilic
addition
dimethylsulfoxonium
methylide
to
amide
bond
in
acyclic
twisted
under
exceedingly
mild
room
temperature
conditions.
A
variety
can
be
employed,
and
protocol
applied
late-stage
derivatization
pharmaceuticals.
Mechanistic
studies
outline
relative
order
reactivity
amides.
Chemistry - A European Journal,
Год журнала:
2022,
Номер
29(1)
Опубликована: Окт. 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.
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
