Quinazolinone-to-Isoquinoline Metamorphosis by Ruthenium-Catalyzed [4+2] Annulation with Sulfoxonium Ylides
Organic Letters,
Год журнала:
2024,
Номер
26(50), С. 10951 - 10957
Опубликована: Дек. 10, 2024
Molecular
editing
of
quinazolinones
to
isoquinolines
by
a
novel
ruthenium-catalyzed
[4+2]
annulation
with
sulfoxonium
ylides
has
been
developed.
The
method
permits
the
precise
and
rapid
assembly
multisubstituted
aminoisoquinolines,
class
heterocycles
that
play
privileged
role
in
organic
synthesis
pharmaceutical
development.
This
new
catalytic
process
exhibits
programmability,
including
directed
C–H
acetylation,
nucleophilic
cyclization,
alcoholysis.
Remarkably,
various
2-arylquinazolinones
could
be
employed
excellent
yields
broad
functional
group
tolerance.
heterocycle-to-heterocycle
protocol
is
compatible
green
chemistry
using
an
EtOH
solvent
releasing
H2O
dimethyl
sulfoxide
as
byproducts.
Язык: Английский
Comparison of Phosphonium and Sulfoxonium Ylides in Ru(II)-Catalyzed Dehydrogenative Annulations: A Density Functional Theory Study
Molecules,
Год журнала:
2025,
Номер
30(9), С. 1883 - 1883
Опубликована: Апрель 23, 2025
Density
functional
theory
calculations
have
been
performed
to
explore
the
detailed
mechanism
of
a
ruthenium-catalyzed
dehydrogenative
annulation
between
α-carbonyl
phosphonium
ylide
(A)
and
sulfoxonium
(B).
The
proposed
catalytic
cycles
consist
several
elementary
steps
in
succession,
namely
C–H
activation
A,
insertion
B,
reductive
elimination,
protodemetallation,
an
intramolecular
Wittig
reaction,
which
is
rate-limiting,
with
free
energy
barrier
31.7
kcal/mol.
As
A
B
are
both
capable
being
substrate
carbene
precursor,
there
potentially
four
competing
pathways
including
homo-coupling
reactions.
Further
demonstrate
that
more
reactive
step
than
while
opposite
conclusion
true
for
step,
can
successfully
explain
fact
solely
observed
product
originated
from
use
as
precursor.
Molecular
electrostatic
potential,
charge
decomposition,
electron
density
difference
analyses
were
understand
distinct
behaviors
two
ylides
nature
key
ruthenium–carbene
intermediate.
Язык: Английский
LiBr-Promoted Reaction of β-Ketodithioesters and Thioamides with Sulfoxonium Ylides to Synthesize Functionalized Thiophenes
Organic Letters,
Год журнала:
2024,
Номер
26(43), С. 9401 - 9406
Опубликована: Окт. 22, 2024
An
operationally
simple
and
highly
efficient
synthesis
of
functionalized
thiophenes
has
been
developed
by
LiBr
promoted
heteroannulation
β-ketodithioesters
thioamides
with
bench-stable
sulfoxonium
ylides
in
open
air
for
the
first
time.
This
one-pot
strategy
involves
formal
Csp3–H
bond
insertion/intramolecular
cyclization
cascade,
featuring
readily
accessible
starting
materials,
TM
additive-free
condition,
broad
substrate
scope,
high
functional
group
compatibility,
scalability.
Moreover,
carbonyl,
thiomethyl,
amino
groups
resulting
thiophene
provide
a
good
handle
on
downstream
transformations.
Язык: Английский