European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(35)
Published: July 27, 2023
Abstract
A
Friedel–Crafts
reaction
of
indolizines
with
2‐aryl‐3
H
‐indol‐3‐ones
catalyzed
by
B(C
6
F
5
)
3
is
described.
This
protocol
gives
access
to
indolizine
derivatives
that
are
valuable
building
blocks
in
synthetic
and
pharmaceutical
chemistry.
The
proceeds
under
mild
conditions,
affording
various
C2‐quaternary
indolin‐3‐ones
based
on
high
yields
regioselectivities.
Moreover,
the
transformations
target
products
were
realized
N‐methylation
trifluoromethane
sulfonation.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 11, 2024
Abstract
Among
the
nucleophilic
oxidants
employed
in
gold‐catalysed
oxidation
of
alkynes,
sulphur‐based
reagents
have
played
a
substantial
role
since
beginning,
granting
access
to
respective
gold
carbene
intermediates.
Herein,
we
describe
first
example
substance
class
sulfoximines
being
used
as
atom
transfer
alkynes
catalysis.
Based
on
transformation
N
‐(2‐alkynylphenyl)
3
H
‐indol‐3‐ones,
it
is
demonstrated
that
sulfoximine
functionality
capable
selectively
transferring
its
nitrogen
moiety
alkyne,
forming
α‐imino
carbene,
which
then
oxidised
by
released
sulfoxide
second
step
via
pseudo‐intramolecular
mechanism—a
distinctive
feature
differentiates
this
work
mechanistically
from
earlier
studies.
A
combination
extensive
experimental
and
theoretical
studies
provides
evidence
for
mechanistic
rationale.
As
no
external
1,2‐difunctionalisation
alkyne
unit
are
required,
wide
variety
functional
groups
tolerated
transformation,
affording
desired
‐indol‐3‐ones
mostly
good
yields.
It
was
further
also
showcased
possible
combine
our
methodology
with
additional
transformations
‐indol‐3‐one
core
one‐pot
procedures,
allowing
facile
C2‐quaternary
indolin‐3‐one
structures.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 11, 2024
Abstract
Unter
den
nukleophilen
Oxidationsmitteln,
die
bei
der
goldkatalysierten
Oxidation
von
Alkinen
eingesetzt
werden,
haben
schwefelbasierte
Reagenzien
Beginn
an
eine
wesentliche
Rolle
gespielt
und
ermöglichten
Zugang
zu
jeweiligen
Goldcarben
Intermediaten.
Wir
beschreiben
hier
das
erste
Beispiel
für
Verwendung
Substanzklasse
Sulfoximine
als
Atomtransferreagenzien
in
Goldkatalyse.
Anhand
Umwandlung
N
‐(2‐Alkinylphenyl)‐sulfoximinen
3
H
‐Indol‐3‐onen
wird
gezeigt,
dass
Sulfoximinfunktionalität
dazu
Lage
ist,
unter
Ausbildung
des
α‐Imino‐Goldcarbens
zunächst
Stickstoffeinheit
selektiv
auf
Alkin
übertragen,
welches
dann
einem
zweiten
Schritt
durch
freigesetzte
Sulfoxid
pseudo‐intramolekularen
Mechanismus
oxidiert
‐
Besonderheit,
diese
Arbeit
mechanistisch
früheren
Studien
unterscheidet.
Eine
Kombination
aus
umfangreichen
experimentellen
theoretischen
liefert
Beweise
zugrundeliegenden
Mechanismus.
Da
keine
externen
1,2‐Difunktionalisierung
Alkins
erforderlich
sind,
Vielzahl
funktioneller
Gruppen
toleriert,
so
gewünschten
‐Indol‐3‐one
meist
guter
Ausbeute
erhalten
werden.
Darüber
hinaus
wurde
es
möglich
unsere
Methodik
mit
weiteren
Transformationen
‐Indol‐3‐on
Kerns
Eintopfverfahren
kombinieren,
was
einen
einfachen
C2‐quartären
Indolin‐3‐on
Strukturen
ermöglicht.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(35)
Published: July 27, 2023
Abstract
A
Friedel–Crafts
reaction
of
indolizines
with
2‐aryl‐3
H
‐indol‐3‐ones
catalyzed
by
B(C
6
F
5
)
3
is
described.
This
protocol
gives
access
to
indolizine
derivatives
that
are
valuable
building
blocks
in
synthetic
and
pharmaceutical
chemistry.
The
proceeds
under
mild
conditions,
affording
various
C2‐quaternary
indolin‐3‐ones
based
on
high
yields
regioselectivities.
Moreover,
the
transformations
target
products
were
realized
N‐methylation
trifluoromethane
sulfonation.
