Acta Scientific Pharmaceutical Sciences,
Год журнала:
2023,
Номер
unknown, С. 37 - 47
Опубликована: Июнь 1, 2023
The
mechanism
is
investigated
for
Pd-catalyzed
carbo-aminative
cyclization
of
1,6-enyne
with
2-iodoaniline.The
regioselective
addition
Pd-inserted
2-iodoaniline
across
alkyne
and
intermolecular
insertion
olefin
leads
to
alkyne-to-alkene
adducts.After
isomerization,
a
pallado
intermediate
obtained
upon
aza-conjugate
addition.The
β-hydride
eliminated
the
help
Pd.The
oxidative
aromatization
promoted
by
carbonate
ion
makes
oxidation
level
consistent
desired
product.The
regioselectivity
6-endo-trig
determined
through
superiority
over
other
two
modes
in
Heck-type
intramolecular
coupling.The
promotion
active
Pd(0)
lies
barrier
decrease
rate-limiting
isomerization
especially
elimination.These
results
are
supported
Multiwfn
analysis
on
FMO
specific
TSs
MBO
value
vital
bonding,
breaking.
Chemical Communications,
Год журнала:
2023,
Номер
59(67), С. 10137 - 10140
Опубликована: Янв. 1, 2023
Selective
annulations
of
alkynes
represent
a
powerful
tool
for
constructing
multicyclic
scaffolds
while
installing
desired
substitution
patterns
with
precision.
Herein,
we
report
Rh-catalyzed
unique
annulation
indolyl
oxopropanenitrile
hydroxy-alkynoates
to
access
pyranoindole
cyclic
motifs,
featuring
enol
oxygen
as
rare
chemoselective
reactive
terminal.
The
reaction
proceeds
via
five-membered
oxy-rodacycle
through
C-H
activation
by
rhodium
complex
guided
enolic-
and
propargyloxy
dual
co-ordination
enable
regio-
stereoselective
modular
assembly.
Organic & Biomolecular Chemistry,
Год журнала:
2022,
Номер
20(13), С. 2609 - 2614
Опубликована: Янв. 1, 2022
Metal-catalyzed
cyclizative
cross-coupling
reactions
have
attracted
enormous
attention
due
to
their
unique
cascade
nature.
We
demonstrated,
herein,
a
dual-cyclizative
coupling
of
ynone
oxime
ethers
with
acrylamides
for
the
synthesis
methylene-linked
isoxazolyl
2-oxindoles.
The
was
triggered
by
palladium(II)-catalyzed
ether
cyclization,
which
underwent
Heck-type
intercepted
an
aryl
iodide
insertion.
Control
experiments
were
carried
out
understand
mechanism.
Organic & Biomolecular Chemistry,
Год журнала:
2022,
Номер
20(32), С. 6363 - 6367
Опубликована: Янв. 1, 2022
A
cascade
reaction
of
enynones
with
enaminones
via
cyclative
coupling
to
engineer
diverse
multisubstituted
furans
and
furano-pyrrole
bisheterocycles
is
described
proposed
involve
carbene
insertion
C–C
migrations
deliver
a
totally
rearranged
product.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
unknown
Опубликована: Март 20, 2024
Abstract
We
report
herein
a
palladium‐catalyzed,
site‐selective
cyclative
annulation
of
o
‐alkynyl
arylamides
with
maleimide
for
the
stereoselective
construction
succinimide‐fused
benzoxazine
derivatives.
This
operationally
simple
and
modular
protocol
provides
access
to
polycyclic
frameworks.
The
other
associated
features
are
high
functional
group
compatibility,
gram‐scale
synthetic
potential,
downstream
transformations.
Control
labeling
experiments
were
conducted
get
insights
into
mechanism.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(70)
Опубликована: Окт. 11, 2023
Although
challenging,
the
distant
C-H
functionalization
with
precision
is
quite
rewarding
and
has
long
been
intriguing.
Tailoring
an
appropriate
template
accomplishes
job
but
prerequisite
sets
limitation.
We
herein
unveil
our
discovery
of
annulation
alkynes
on
to
two
(from
directing
group)
bonds
through
rollover
cyclometallation
assisted
by
conjugated
C=C
bond.
The
follows
a
concomitant
cyclization
rare
triple
functionalization.
totally
regioselective
array
unsymmetrical
alkynes,
taking
leverage
extended
conjugation
or
tertiary
hydroxyl
co-ordination.
mechanism
supported
control
experiments,
KIE
&
labelling
studies
Mass
spectrometry.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
30(7)
Опубликована: Ноя. 6, 2023
Reaching
the
formidable
C-H
corners
has
been
one
of
top
priorities
organic
chemists
in
recent
past.
This
prompted
us
to
disclose
herein
a
vicinal
annulation
2-iodo
benzoates,
indoles,
and
carbazoles
with
N-embedded
1,6-enynes
through
7-/8-membered
palladacycles.
The
relay
does
not
require
assistance
any
directing
group,
leading
multicyclic
scaffolds,
which
are
readily
diversified
an
array
adducts
(with
new
functional
tethers
and/or
three
contiguous
stereocenters),
we
showcase
rare
benzylic
mono-oxygenation.
Angewandte Chemie,
Год журнала:
2022,
Номер
135(12)
Опубликована: Дек. 30, 2022
Abstract
The
C−H
functionalization
strategy
provides
access
to
valuable
molecules
that
previously
required
convoluted
synthetic
attempts.
Dual
unsymmetrical
functionalization,
with
a
single
bifunctional
reagent,
is
an
effective
tactic.
Propargyl
alcohols
(PAs),
despite
containing
reactive
C≡C
bond,
have
not
been
explored
as
building
blocks
via
oxidative
cleavage.
Annulations
activation
are
versatile
and
synthetically
attractive
strategy.
We
disclose
PA
new
reagent
for
dual
of
biphenylamine
regioselectively
annulated
outcomes.
On
tuning
the
conditions,
annulation
bifurcated
towards
unusual
cyclization.
This
method
accommodates
wide
range
PAs
showcases
late‐stage
diversification
some
natural
products.
Acta Scientific Pharmaceutical Sciences,
Год журнала:
2023,
Номер
unknown, С. 37 - 47
Опубликована: Июнь 1, 2023
The
mechanism
is
investigated
for
Pd-catalyzed
carbo-aminative
cyclization
of
1,6-enyne
with
2-iodoaniline.The
regioselective
addition
Pd-inserted
2-iodoaniline
across
alkyne
and
intermolecular
insertion
olefin
leads
to
alkyne-to-alkene
adducts.After
isomerization,
a
pallado
intermediate
obtained
upon
aza-conjugate
addition.The
β-hydride
eliminated
the
help
Pd.The
oxidative
aromatization
promoted
by
carbonate
ion
makes
oxidation
level
consistent
desired
product.The
regioselectivity
6-endo-trig
determined
through
superiority
over
other
two
modes
in
Heck-type
intramolecular
coupling.The
promotion
active
Pd(0)
lies
barrier
decrease
rate-limiting
isomerization
especially
elimination.These
results
are
supported
Multiwfn
analysis
on
FMO
specific
TSs
MBO
value
vital
bonding,
breaking.
