Boosting N-Heterocyclic Carbene Radical Organocatalysis with Nickel Chemistry: A Rational Mechanistic Study-Based Approach
ACS Catalysis,
Год журнала:
2024,
Номер
14(9), С. 7149 - 7156
Опубликована: Апрель 23, 2024
A
cooperative
NHC/nickel
catalytic
methodology
has
been
developed
for
the
synthesis
of
ketones
employing
aromatic
aldehydes
and
tertiary
alkyl
iodides.
All
key
steps
postulated
cycle
were
validated
with
comprehensive
stoichiometric
electrochemical
studies,
including
reduction
NiII
by
deprotonated
Breslow
intermediate,
Ni0
promoted
halogen-atom
abstraction
to
generate
transient
radicals,
coupling
between
latter
persistent
acyl
thiazolium
radical
intermediate.
Such
a
broadly
proposed
accepted,
yet
elusive,
intermediate
isolated
studied
single-crystal
X-ray
diffraction
study.
Язык: Английский
Regioselective Synthesis of Thiazole‐5‐thione Based on [2 + 3] Annulation Trapping of α‐Keto Sulfine with Thioamide
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 22, 2024
Abstract
Aiming
to
develop
novel
annulation
reactions
using
sulfine
intermediates,
we
have
established
a
regioselective
formal
[2+3]
cyclization
reaction
of
α
‐keto
sulfines
generated
from
the
elimination
arylacyl
sulfoxides
and
thioamides.
This
new
strategy
allows
for
synthesis
thiazole‐5‐thiones
directly
without
catalysts
or
additives.
The
approach
features
step‐economic,
one‐pot
characteristics
via
tandem
sequence
in
situ
generation,
regiospecifically
nucleophilic
attack
[3+2]
cyclizatoin,
dithioate
(S=C−S−)
skeletons
formation,
subsequent
intramolecular
cyclization.
also
represents
method
constructing
skeletons.
Язык: Английский