Advanced Synthesis & Catalysis,
Journal Year:
2021,
Volume and Issue:
363(13), P. 3311 - 3317
Published: May 8, 2021
Abstract
A
method
to
synthesize
pyrazolo[1,2‐a]cinnolines
via
rhodium(III)‐catalyzed
C−H
activation
of
pyrazolidinones
and
subsequent
[4+2]
annulation
sulfoxonium
ylides
was
developed.
5‐Substituted
or
5,10‐disubstituted
could
be
obtained
by
slightly
adjusting
the
reaction
conditions.
Gram‐scale
synthesis
practical
transformations
proved
practicability
this
method.
The
mechanism
proposed
in
article
on
basis
preliminary
mechanistic
results
previous
reports.
This
features
simplified
operation,
metal‐oxidant
free,
readily
available
reactants.
magnified
image
Organic & Biomolecular Chemistry,
Journal Year:
2020,
Volume and Issue:
18(43), P. 8793 - 8809
Published: Jan. 1, 2020
Sulfur
ylides
first
disclosed
in
1930
started
to
gain
more
attention
the
1960s,
thanks
mainly
studies
by
Corey
and
Chaykovsky
on
their
use
for
preparation
of
strained
rings.
More
recently,
chemistry
these
compounds
has
experienced
important
growth,
part
due
similarity
reactivities
with
diazo
compounds.
This
short
review
provides
an
overview
great
assortment
reactions
sulfoxonium
ylides,
outlining
a
comparison
between
congeners:
sulfonium
Insertion
reactions,
cyclisation
ring-opening
are
highlighted,
giving
particular
catalytic
asymmetric
methodologies.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(33), P. 14384 - 14390
Published: July 22, 2020
Herein
we
disclose
a
new
catalytic
asymmetric
approach
for
the
synthesis
of
chiral
α-amino
ketones,
which
is
particularly
useful
less
accessible
acyclic
α-tertiary
cases.
By
protonation–amination
sequence,
our
represents
rare
H–heteroatom
bond
insertion
by
α-carbonyl
sulfonium
ylides,
an
attractive
surrogate
diazocarbonyls.
The
mild
intermolecular
C–N
formation
was
catalyzed
phosphoric
acids
with
excellent
efficiency
and
enantioselectivity.
products
are
precursors
to
other
important
amine
derivatives,
including
drug
molecules
ligands.
enantioselectivity
controlled
dynamic
kinetic
resolution
in
amination
step,
rather
than
initial
protonation.
This
process
opens
up
platform
development
related
reactions.
Chemical Science,
Journal Year:
2021,
Volume and Issue:
13(5), P. 1192 - 1209
Published: Dec. 8, 2021
Sulfoxonium
ylides
are
important
surrogates
for
diazo
compounds,
and
their
use
in
industry
as
safer
alternatives
has
been
evaluated
during
recent
years.
Beyond
the
known
classical
transformations,
these
have
also
used
a
surprising
plethora
of
novel
intrinsic
chemical
reactions,
especially
Bench
stability
handling
an
advantage
this
class
organosulfur
molecules.
Despite
this,
efficient
asymmetric
specifically
catalytic
enantioselective
versions,
only
recently
reported,
there
specific
reasons
this.
This
perspective
article
covers
topic
from
first
studies
up
to
latest
advances,
giving
personal
perspectives
showing
main
challenges
area
coming
Chemical Science,
Journal Year:
2022,
Volume and Issue:
14(4), P. 843 - 848
Published: Nov. 29, 2022
While
asymmetric
insertion
of
metal
carbenes
into
H-X
(X
=
C,
N,
O,
etc.)
bonds
has
been
well-established,
control
over
free
is
challenging
due
to
the
presence
strong
background
reactions
and
lack
any
anchor
for
a
catalyst
interaction.
Here
we
have
achieved
first
photo-induced
metal-free
bond
this
type.
With
visible
light
used
as
promoter
chiral
phosphoric
acid
catalyst,
α-diazoesters
aryl
amines
underwent
smooth
N-H
form
enantioenriched
α-aminoesters
with
high
efficiency
good
enantioselectivity
under
mild
conditions.
Key
success
was
use
DMSO
an
additive,
which
served
rapidly
capture
highly
reactive
carbene
intermediate
domesticated
sulfoxonium
ylide.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(36), P. 15554 - 15559
Published: April 30, 2020
Abstract
The
first
example
of
enantioselective
S−H
insertion
reactions
sulfoxonium
ylides
is
reported.
Under
the
influence
thiourea
catalysis,
excellent
levels
enantiocontrol
(up
to
95
%
ee
)
and
yields
97
%)
are
achieved
for
31
examples
in
aryl
thiols
α‐carbonyl
ylides.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(3), P. 1038 - 1043
Published: Jan. 21, 2021
A
ruthenium-catalyzed
highly
chemoselective
N-alkylation
of
2-pyridones
has
been
developed,
affording
N-alkylated
2-pyridone
derivatives
in
good
yields
and
excellent
N-selectivity.
The
key
to
achieve
this
unprecedented
N–H
rather
than
O–H
insertion
reaction
is
the
use
CpRu(PPh3)2Cl
as
catalyst
sulfoxonium
ylides
alkylation
reagents.
Moreover,
protocol
also
amenable
7-azaindoles
by
slightly
varying
conditions.
Furthermore,
sulfonium
are
suitable
reagents,
providing
selectivity.
Chemical Science,
Journal Year:
2021,
Volume and Issue:
12(33), P. 11191 - 11196
Published: Jan. 1, 2021
An
organocatalytic
asymmetric
N–H
insertion
reaction
of
α-carbonyl
sulfoxonium
ylides
has
been
developed
to
provide
efficient
access
α-amino
esters
without
involving
a
metal
carbenoid
intermediate.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(23), P. 4286 - 4291
Published: June 2, 2023
Two
categories
of
tetrasubstituted
phenols
were
prepared
via
the
cycloaddition
reaction
vinyl
sulfoxonnium
ylides
with
cyclopropenones
in
a
switchable
manner.
Copper
carbenoid
was
proposed
as
active
intermediate
process
2,3,4,5-tetrasubstituted
formation,
while
2,3,5,6-tetrasubstituted
generated
direct
[3
+
3]
annulation
under
metal-free
conditions.
Further
synthetic
applications
also
demonstrated.
