Abstract
Over
the
past
two
decades,
transition-metal-catalyzed
C–H
activation
and
subsequent
oxidative
cyclization
with
alkynes
or
their
surrogates
has
emerged
as
a
powerful
synthetic
tool
for
fused
heteroaromatics.
We
report
Rh(III)-catalyzed
annulation
ring-opening
cascade
reaction
2-aryloxazolines.
By
utilizing
vinyl
selenone
an
oxidizing
acetylene
surrogate,
target
three-component
coupling
products
were
obtained
in
high
yields
without
using
stoichiometric
amount
of
external
oxidant.
Science,
Год журнала:
2024,
Номер
383(6684), С. 750 - 756
Опубликована: Фев. 15, 2024
Water
can
accelerate
a
variety
of
organic
reactions
far
beyond
the
rates
observed
in
classical
solvents.
However,
using
pure
water
as
solvent
introduces
solubility
constraints
that
have
limited
applicability
efficient
photochemistry
particular.
We
report
here
formation
aggregates
between
pairs
arenes,
heteroarenes,
enamines,
or
esters
with
different
electron
affinities
an
aqueous
medium,
leading
to
oil-water
phase
boundary
through
substrate
melting
point
depression.
The
active
hydrogen
atoms
reactants
engage
bonds
water,
thereby
accelerating
photochemical
reactions.
This
methodology
realizes
appealingly
simple
conditions
for
coupling
complex
solid
molecules,
including
drug
molecules
are
poorly
soluble
water.
Chemical Communications,
Год журнала:
2022,
Номер
58(28), С. 4476 - 4479
Опубликована: Янв. 1, 2022
A
ruthenium-catalyzed
oxidative
coupling
of
vinylene
carbonate
with
isoxazoles
has
been
developed
to
achieve
the
direct
C-H
formylmethylation
a
diverse
array
arylisoxazoles
utilizing
isoxazole
ring
as
directing
group.
simple
manipulation
established
reaction
conditions
leads
formation
fused-anthranils.
Importantly,
functions
both
formylmethyl
cation
equivalent
through
decarboxylation
process
and
an
acetylene
equivalent.
Control
experiments
were
conducted
elucidate
plausible
mechanism.
This
methodology
is
expected
provide
facile
expeditious
approach
for
synthesis
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(22), С. 5717 - 5734
Опубликована: Янв. 1, 2023
Vinylene
carbonate
(VC)
has
emerged
as
a
promising
coupling
partner
to
participate
in
various
attractive
C–H
conversions
and
implement
an
increasing
number
of
novel
reactions.
In
this
review,
we
provide
summary
the
advancements
achieved
metal-catalyzed
functionalization
using
VC.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(9), С. 1457 - 1464
Опубликована: Апрель 14, 2023
Abstract
In
this
study,
Rh(III)‐catalyzed
C−H
bifunctionalization
and
direct
vinylene
annulation
of
sulfoxonium
ylides
N
‐carbamoylindoles
with
carbonate
was
accomplished,
which
afforded
a
series
naphthalenones
containing
β‐ketosulfoxonium
ylide
moiety,
isocoumarins,
pyrimidones.
This
protocol
featured
mild
conditions,
broad
substrate
scope,
functional‐groups
compatibility.
addition,
related
applications
preliminary
mechanistic
exploratory
were
also
investigated
magnified
image
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(20), С. 3400 - 3412
Опубликована: Сен. 6, 2023
Abstract
Recently,
vinylene
carbonate
has
been
developed
as
a
powerful
synthon
in
transition
metal‐catalyzed
C−H
bond
activation/cyclization
reactions.
This
review
introduces
recent
progress
the
use
of
reactant,
by
analyzing
and
comparing
reaction
models
involving
surrogate
ethynol,
acetylene,
acetylation
reagents
or
other
reactants,
while
addressing
related
mechanisms
synthetic
applications.
Organic Letters,
Год журнала:
2023,
Номер
25(18), С. 3206 - 3209
Опубликована: Май 4, 2023
Isoquinoline
is
a
privileged
structure
in
many
bioactive
compounds
and
valuable
ligands.
Transition-metal-catalyzed
oxidative
annulation
of
imine
derivatives
has
become
promising
synthetic
method;
however,
catalytic
synthesis
3,4-nonsubstituted
isoquinolines
by
formal
acetylene
been
scarce
to
date.
Herein,
we
introduce
vinyl
selenone
as
an
effective
surrogate
for
the
Rh-catalyzed
annulative
coupling
under
mild
conditions.
The
Se
fragment
can
be
recovered
diselenide
recycled.
product
readily
converted
1-aminoisoquinolines.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(44)
Опубликована: Сен. 27, 2023
Abstract
A
mild
and
convenient
synthesis
of
3,4‐unsubstituted
isoquinolones
has
been
achieved
from
N
‐methoxybenzamides
vinylene
carbonate
as
an
acetylene
surrogate
with
a
versatile
rhodium(III)
catalyst.
The
reaction
proceeded
at
room
temperature
in
biomass
derived
ethanol
solvent.
This
protocol
avoids
the
use
stoichiometric
external
oxidant,
served
internal
oxidant.
C−H/N−H
activation
annulation
manifold
broad
substrate
scope
excellent
levels
regioselectivities.
preliminary
mechanistic
studies
suggest
facile
reversible
chelation‐assisted
C−H
rhodation.
Diversification
provide
access
to
4‐substituted
isoquinolines,
which
are
complementary
previously
reported
protocols.
Catalysts,
Год журнала:
2022,
Номер
12(10), С. 1163 - 1163
Опубликована: Окт. 2, 2022
N-heterocycles
are
ubiquitous
in
natural
products,
pharmaceuticals,
organic
materials,
and
numerous
functional
molecules.
Among
the
current
synthetic
approaches,
transition
metal-catalyzed
C–H
functionalization
has
gained
considerable
attention
recent
years
due
to
its
advantages
of
simplicity,
high
atomic
economy,
ready
availability
starting
materials.
In
field
N-heterocycle
synthesis
via
functionalization,
nickel
been
recognized
as
one
most
important
catalysts.
this
review,
we
will
introduce
nickel-catalyzed
intramolecular
intermolecular
pathways
for
from
2008
2021.
RSC Medicinal Chemistry,
Год журнала:
2023,
Номер
14(12), С. 2509 - 2534
Опубликована: Янв. 1, 2023
This
review
will
be
an
essential
toolbox
for
medicinal
and
bioorganic
chemists
seeking
novel
multifunctional
hybrid
bioactive
N-heterocycles
drug
discovery.
The
work
highlights
the
need
relevance
of
unexplored
bioisosterism
employing
isoquinoline-based
small-molecules
in
design.
