The
rare
[1,2]-sigmatropic
rearrangement
of
sulfoxonium-iodonium
hybrid
ylides
is
described,
which
enables
the
efficient
sulfoxidation/sulfonylation-alkylation
I(III)/S(VI)
with
1,3-dicarbonyls.
By
slight
modification
reaction
conditions,
controllable
alkylation-hydroxylation
and
dialkylation
were
achieved.
This
strategy
affords
a
diverse
array
α,α-difunctionalized
ketones
in
moderate
to
good
yields,
demonstrating
broad
substrate
scope.
These
findings
provide
an
important
advancement
sulfoxonium
highlight
divergent
reactivity
ylides.
Chemical Reviews,
Год журнала:
2022,
Номер
122(15), С. 12544 - 12747
Опубликована: Июль 17, 2022
1,1,1,3,3,3-Hexafluoroisopropanol
(HFIP)
is
a
polar,
strongly
hydrogen
bond-donating
solvent
that
has
found
numerous
uses
in
organic
synthesis
due
to
its
ability
stabilize
ionic
species,
transfer
protons,
and
engage
range
of
other
intermolecular
interactions.
The
use
this
exponentially
increased
the
past
decade
become
choice
some
areas,
such
as
C–H
functionalization
chemistry.
In
review,
following
brief
history
HFIP
an
overview
physical
properties,
literature
examples
reactions
using
or
additive
are
presented,
emphasizing
effect
each
reaction.
Organic & Biomolecular Chemistry,
Год журнала:
2020,
Номер
18(43), С. 8793 - 8809
Опубликована: Янв. 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.
Chemical Science,
Год журнала:
2021,
Номер
13(5), С. 1192 - 1209
Опубликована: Дек. 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
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(37), С. 14962 - 14968
Опубликована: Сен. 8, 2021
A
NiH-catalyzed
thioether-directed
cyclometalation
strategy
is
developed
to
enable
remote
methylene
C–H
bond
amidation
of
unactivated
alkenes.
Due
the
preference
for
five-membered
nickelacycle
formation,
chain-walking
isomerization
initiated
by
NiH
insertion
an
alkene
can
be
terminated
at
γ-methylene
site
from
moiety.
By
employing
2,9-dibutyl-1,10-phenanthroline
(L4)
as
ligand
and
dioxazolones
reagent,
occurs
γ-C(sp3)–H
bonds
afford
amide
products
in
up
90%
yield
(>40
examples)
with
remarkable
regioselectivity
(up
24:1
rr).
New Journal of Chemistry,
Год журнала:
2021,
Номер
45(31), С. 13692 - 13746
Опубликована: Янв. 1, 2021
This
review
summarises
a
wide
range
of
transformations
on
the
indole
skeleton,
including
arylation,
alkenylation,
alkynylation,
acylation,
nitration,
borylation,
and
amidation,
using
transition-metal
catalyzed
C–H
functionalization
as
key
step.
Chemistry - An Asian Journal,
Год журнала:
2021,
Номер
16(5), С. 443 - 459
Опубликована: Янв. 15, 2021
Metal
carbenes
play
a
pivotal
role
in
transition-metal-catalyzed
synthetic
transfer
reactions.
The
metal
carbene
is
generated
either
from
diazo
compound
through
facile
extrusion
of
N2
with
catalyst
or
situ
other
sources
like
triazoles,
pyriodotriazoles,
sulfoxonium
ylides
and
iodonium-ylide.
On
the
hand,
Co(III),
Rh(III)
&
Ir(III)-catalyzed
C-H
functionalizations
have
been
well
established
as
key
step
to
enable
construction
various
transformations.
Interestingly,
recent
years,
merging
these
two
concepts
activation
migratory
insertion
gained
much
attention,
particular
group
9
metal-catalyzed
arene
precursors
via
insertion.
In
this
review,
we
summarize
advances
direct
alkylation/alkenylation/arylation
also
discuss
intermediates
within
catalytic
cycles.
Asian Journal of Organic Chemistry,
Год журнала:
2022,
Номер
11(4)
Опубликована: Март 23, 2022
Abstract
In
recent
years,
the
transition‐metal‐catalyzed
functionalization
reactions
of
sulfoxonium
ylides
have
been
explored
extensively
because
their
usefulness
as
carbene‐transfer
agents,
since
they
can
produce
metal
carbenes
through
catalysis.
Moreover,
are
safer
and
advantages
simple
handling
good
stability
over
other
counterparts
like
diazo‐compounds.
This
review
article
attempts
to
highlight
advances
in
metal‐catalyzed
C−H
ylides.
Chemistry - An Asian Journal,
Год журнала:
2020,
Номер
15(24), С. 4184 - 4198
Опубликована: Ноя. 9, 2020
Selective
editing
of
the
benzenoid
C-H
bonds
(C4-C7)
in
indoles/indolines
has
received
great
interest
because
functionalized
are
featured
many
marketed
drugs
and
natural
products.
Transition-metal-catalyzed
directed
functionalization
thus
been
developed
to
manipulate
core
through
C-C
C-heteroatom
bond
formation.
This
review
covers
recent
advances
selective
forming
reactions,
alkylation,
alkenylation
alkynylation,
over
ring
using
metal
catalysis.
Organic Letters,
Год журнала:
2021,
Номер
23(3), С. 1038 - 1043
Опубликована: Янв. 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.
