Research Square (Research Square),
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 16, 2024
Abstract
Multi-component
multi-functionalization
reactions
involving
active
intermediates
are
powerful
tools
for
rapidly
generating
a
wide
array
of
compounds.
Metal
carbynoids,
with
their
distinct
reactivity,
hold
great
promise
developing
new
synthetic
methodologies.
However,
application
in
catalytic
transfer
has
been
hindered
by
the
limited
availability
suitable
precursors.
In
this
study,
we
investigate
potential
α-halo
Rh-carbenes,
leveraging
concept
metal
carbynoids
reactions.
Through
chiral
phosphoric
acid-catalyzed
asymmetric
trifunctionalization,
have
developed
an
innovative
method
synthesizing
variety
α-cyclic
ketal
β-amino
esters
high
yields
and
excellent
enantioselectivity.
Our
extensive
experimental
computational
studies
reveal
that
Rh-carbenes
exhibit
carbynoid
properties,
which
facilitate
transformation
into
functionalized
Fischer-type
through
decomposition
C-halo
bond.
Organic Letters,
Год журнала:
2024,
Номер
26(12), С. 2511 - 2516
Опубликована: Март 20, 2024
This
work
demonstrates
the
synthesis
of
a
variety
perfluoroalkyl
heterocycles
via
visible-light-driven
radical-polar
crossover
cyclization
strategy.
In
this
process,
single-electron
reduction/SNV-type/cyclization
sequences
follow
radical
addition
reaction
diazoester,
which
differs
from
current
role
diazoesters
as
precursors/acceptors.
transformation
excellent
functional
group
compatibility
and
allows
for
modification
many
bioactive
molecules
with
diazoesters.
Such
could
represent
novel
approach
to
photochemical
diazo
compounds.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(13)
Опубликована: Янв. 18, 2024
Abstract
Trifluoromethyl
cationic
carbyne
(CF
3
C
+
:)
possessing
dual
carbene‐carbocation
behavior
emulated
as
trifluoromethyl
metal‐carbynoid
=M)
has
not
been
explored
yet,
and
its
reaction
characteristics
are
unknown.
Herein,
a
novel
α‐diazotrifluoroethyl
sulfonium
salt
was
prepared
used
in
Rh‐catalyzed
three‐component
[2+1+2]
cycloadditions
for
the
first
time
with
commercially
available
N
‐fused
heteroarenes
nitriles,
yielding
series
of
imidazo[1,5‐
]
‐heterocycles
that
interest
medicinal
chemistry,
which
insertion
Rh‐carbynoid
=Rh)
into
C=N
bonds
involved.
This
strategy
demonstrates
synthetic
applications
late‐stage
modification
pharmaceuticals,
construction
CD
‐containing
‐heterocycles,
gram‐scale
experiments,
synthesis
phosphodiesterase
10A
inhibitor
analog.
These
highly
valuable
modifiable
exhibit
good
antitumor
activity
vitro,
thus
demonstrating
their
potential
chemistry.
Organic Letters,
Год журнала:
2024,
Номер
26(28), С. 5911 - 5916
Опубликована: Июль 8, 2024
Acylsilanes
are
emerging
bench-stable
reagents
for
the
generation
of
electron-rich
oxycarbenes
that
difficult
to
access
with
unstable
diazo
compounds.
Herein,
we
report
a
siloxycarbene-mediated
stereoselective
synthesis
silyl
enol
ethers
through
visible-light-induced
intermolecular
reactions
between
acylsilanes
and
α,β-unsaturated
ketones.
Both
solvent
low
temperature
important
success
reaction.
This
approach
features
atomic
economics,
exclusive
stereocontrol,
broad
substrate
scope.
The
synthetic
potential
this
methodology
is
demonstrated
by
gram-scale
reaction
various
downstream
transformations
including
requiring
configuration
purity
ethers.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Фев. 7, 2025
Multi-component
multi-functionalization
reactions
involving
active
intermediates
are
powerful
tools
for
rapidly
generating
a
wide
array
of
compounds.
Metal
carbynoids,
with
their
distinct
reactivity,
hold
great
promise
developing
synthetic
methodologies.
However,
application
in
catalytic
transfer
has
been
hindered
by
the
limited
availability
suitable
precursors.
In
this
study,
we
investigate
potential
α-halo
Rh-carbenes,
leveraging
concept
metal
carbynoids
reactions.
Through
chiral
phosphoric
acid-catalyzed
asymmetric
trifunctionalization,
have
developed
method
synthesizing
variety
α-cyclic
ketal
β-amino
esters
high
yields
and
excellent
enantioselectivity.
Our
extensive
experimental
computational
studies
reveal
that
Rh-carbenes
exhibit
carbynoid
properties,
which
facilitate
transformation
into
functionalized
Fischer-type
through
decomposition
C-halo
bond.
European Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 11, 2025
Abstract
Amino
acids
play
significant
roles
in
the
study
of
life
sciences,
pharmaceutical
R&D,
bioengineering,
and
so
on.
Artificial
amino
acid‐based
drugs
are
important
advancing
therapeutic
innovation
for
multiple
diseases
including
chronic
pain,
diabetes,
Alzheimer's
disease.
On
other
hand,
multicomponent
reactions
(MCRs)
demonstrated
to
be
a
powerful
strategy
construction
complicated
structures
from
readily
accessible
starting
reagents
one
pot.
Thus,
applying
preparation
their
derivatives
can
potent
research
chemistry.
With
rapid
development
various
catalytic
methods
reactions,
this
review
outlines
recent
acid
by
transition
metal‐catalyzed,
light‐mediated
organocatalytic
reactions.
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Diazomethyl-λ
3
-iodanes
have
recently
emerged
as
carbyne
equivalents
in
organic
synthesis,
enabling
the
construction
of
multi-substituted
carbon
centers
through
strategic
sequential
activation
diazo
and
iodane
functional
groups.
Distinct
from...
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
Unprecedented
diazoacetate
N
-heteroarenium
salts
are
synthesized
and
participate
in
catalytic
[2
+
1]
cycloadditions
[2,3]-sigmatropic
rearrangements,
providing
facile
access
to
otherwise
difficult-to-obtain
multi-functionalized
-heterocycles.
The
transition
metal-catalyzed
direct
coupling
reac-tions
involving
electron-rich
Fisher
carbene
species
are
largely
underdeveloped
and
remain
a
big
chal-lenge.
Here,
we
report
reaction
of
azoles
with
copper
bearing
an
α-siloxy
group,
which
could
be
in-situ
generated
from
acylsilanes
catalytically
under
photoirradiation
redox-neutral
conditions.
This
features
mild
conditions
remarkable
heterocycle
compat-ibility.
Notably,
this
protocol
tolerates
series
azole
derivatives,
including
benzoxazole,
benzothia-zole,
benzoimidazole,
benzoisoxazole,
oxazole,
oxadi-azole,
triazolo[4,3-a]pyridine,
purine,
caffeine
etc.,
is
highly
synthetic
useful
in
organic
synthesis
pharmaceutical
discovery.
Preliminary
mecha-nistic
studies
kinetic
analysis
implied
bimetal-lic
relay
process.
Advanced Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 14, 2024
Abstract
The
transition
metal‐catalyzed
direct
coupling
reactions
involving
electron‐rich
Fischer
carbene
species
are
largely
underdeveloped
and
remain
a
big
challenge.
Here,
reaction
of
azoles
azine
N
‐oxides
is
reported
with
copper
bearing
an
α
‐siloxy
group
i,
which
can
be
in
situ
generated
from
acylsilanes
catalytically
under
photoirradiation
redox‐neutral
conditions.
This
between
Cu‐carbene
hard
carbanion
nucleophiles
may
undergo
bimetallic
relay
process,
confirmed
by
the
kinetic
analysis
NMR
analysis.
features
mild
conditions
remarkable
heterocycle
compatibility.
Notably,
this
protocol
tolerates
series
azole
or
‐oxide
derivatives,
including
benzoxazole,
benzothiazole,
benzoimidazole,
benzoisoxazole,
oxazole,
oxadiazole,
triazolo[4,3
‐a
]pyridine,
purine,
caffeine,
pyridine
‐oxide,
quinoline
pyrazine
pyridazine
etc.
synthetic
value
approach
demonstrated
efficient
synthesis
histamine
h4
receptor
ligand
marketed
drug
carbinoxamine.
