Cocatalyst-Dependent Divergent Amination of Alkylgold Intermediates with Azodicarboxylates
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 5211 - 5218
Опубликована: Март 12, 2025
The
asymmetric
electrophilic
amination
using
azodicarboxylates
as
the
N-source
for
construction
of
C–N
bond
has
attracted
much
attention
over
past
decades.
However,
use
in
situ
formed
nucleophilic
intermediates,
rather
than
bench-stable
reagents,
remains
elusive
and
challenging.
Herein,
we
disclose
an
enantioselective
reaction
generated
alkylgold
species
with
under
a
gold
complex
chiral
quinine-derived
squaramide
(QN-SQA)
synergetic
catalysis,
leading
to
alkylideneoxazolines
nitrogen-containing
tertiary
carbon
stereocenter
good
high
yields
enantioselectivities.
Moreover,
starting
from
same
oxazoles
incorporating
aminomethyl
group
on
5-position
could
be
obtained
by
Brønsted
acid
relay
catalysis
via
alkylideneoxazoline
species.
This
method
offers
complementary
approach
through
interception
With
this
strategic
protocol,
further
synthetic
applications
can
envisioned
catalytic
C–C
C–X
bonds.
Язык: Английский
Synthesis of Masked 2-Pyridones from 1,3-Enynyl Esters via Tandem Gold-Catalyzed Cycloisomerization and Oxidative Nitrogen Insertion
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 18, 2025
An
efficient
synthetic
method
to
regioselectively
assemble
masked
2-pyridones
that
relies
on
sequential
gold-catalyzed
cycloisomerization
and
phenyliodonium
diacetate
(PIDA)-mediated
oxidative
nitrogen
insertion
from
1,3-enynyl
esters
in
a
one-pot,
two-step
manner
is
described.
The
utility
of
the
cascade
protocol
was
further
demonstrated
by
2
mmol
scale
synthesis
one
example
its
elaboration
other
potentially
useful
building
blocks
as
well
late-stage
modification
diverse
array
structurally
complex
bioactive
molecules.
Язык: Английский
Ruthenium and Iodine Anion Cocatalyzed Cascade Dihalogenation and Cyclization of Internal Alkyne-Tethered Cyclohexadienones with 1,2-Dihaloethanes
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(13), С. 9686 - 9694
Опубликована: Июнь 22, 2024
We
have
established
an
efficient
ruthenium(II)
and
iodine
anion
cocatalyzed
dihalogenation
cascade
cyclization
of
internal
alkyne-tethered
cyclohexadienones,
which
stereoselectively
afforded
numerous
products
with
a
bioactive
hydrobenzofuran
skeleton
in
high
yields
under
mild
conditions.
In
this
transformation,
the
reaction
pathway
was
determined
by
concentration
electrophilic
reagent,
also
provided
strategy
for
control
selectivity.
Furthermore,
method
features
use
1,2-dihaloroethane
as
halogen
source
via
catalyst.
Язык: Английский
Stereoselective Double Spirocyclization of 2-Benzyl-3-alkynyl Chromone with Nitrone via Gold-Catalyzed Cascade Reactions
Organic Letters,
Год журнала:
2024,
Номер
26(31), С. 6675 - 6680
Опубликована: Июль 25, 2024
A
novel,
highly
stereoselective
gold-catalyzed
spirocyclization
of
2-benzyl-3-alkynyl
chromone
with
nitrone
is
described.
This
cascade
reaction
involves
cycloisomerization,
nitrone-olefin
[3
+
2]-annulation,
alkene
oxidation,
and
rearrangement
for
the
formation
spirocyclic
products.
Interestingly,
isoxazolidine
ring
generated
from
2]-annulation
donates
oxygen
to
generate
a
new
pyran-3(4
Язык: Английский
Gold(I)-Catalyzed Rautenstrauch/Hetero-Diels–Alder/Retro-aza-Michael Cascade Reaction for the Synthesis of α-Hydrazineyl-2-cyclopentenones
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 12, 2024
A
one-pot
synthesis
of
ring-fused,
α-hydrazineyl-2-cyclopentenone
derivatives
is
achieved
by
a
gold(I)-catalyzed
Rautenstrauch/hetero
Diels-Alder/ring
opening
tandem
reaction
suitable
propargyl
esters.
By
mixing
the
latter
with
dialkylazodicarboxylate
in
presence
gold(I)
catalyst,
1,2-acyloxy
migration/cyclization
process
(Rautenstrauch
reaction)
leads
to
cyclopentadienyl
ester
intermediates
which
are
trapped
heterodienophile
present
situ.
This
provides
strained
spontaneously
undergo
highly
regioselective
ring
retro
aza-Michael
promoted
eventually
yielding
target
compounds.
Six-
and
seven-membered
ring-fused
cyclopentenones
bearing
pendant
α-hydrazineyl
moiety
can
be
obtained
moderate
excellent
yield
(50-98%)
this
approach,
minimal
erosion
initial
optical
purity
when
using
enantioenriched
substrates.
Язык: Английский
DFT Investigation on Palladium-Catalyzed [2 + 2 + 1] Spiroannulation between Aryl Halides and Alkynes: Mechanism, Base Additive Role, and Solvent and Ligand Effects
Xue Tan,
Wenji Bai,
Yu-Bing Shi
и другие.
The Journal of Physical Chemistry A,
Год журнала:
2024,
Номер
128(42), С. 9135 - 9145
Опубликована: Окт. 11, 2024
Transition
metal-catalyzed
spiroannulations
are
practical
strategies
for
constructing
spirocyclic
skeletons
of
pharmaceutical
and
biological
significance,
yet
the
microscopic
mechanism
still
lacks
in-depth
explorations.
Here,
palladium-catalyzed
[2
+
2
1]
spiroannulation
between
aryl
halides
alkynes
was
studied
by
employing
density
functional
theory
(DFT)
method.
Based
on
comprehensive
explorations
a
couple
possible
reaction
pathways,
it
is
found
that
probably
experiences
C-I
oxidative
addition,
alkyne
migration
insertion,
Cs
Язык: Английский