Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(32)
Опубликована: Май 28, 2024
Abstract
A
photocatalytic
decarboxylative
functionalization
of
cyclopropenes
is
reported.
Starting
from
a
broad
range
redox‐active
ester‐substituted
cyclopropenes,
cyclopropenylphthalimides
can
be
synthesized
in
the
absence
nucleophile.
Alternatively,
different
carbon
and
heteroatom
nucleophiles
introduced.
The
transformation
proceeds
most
probably
through
formation
an
aromatic
cyclopropenium
cation,
followed
by
trapping
with
nucleophiles.
Chemical Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 13, 2024
Hypervalent
iodine(III)
compounds
have
found
wide
application
in
modern
organic
chemistry
as
environmentally
friendly
reagents
and
catalysts.
iodine
are
commonly
used
synthetically
important
halogenations,
oxidations,
aminations,
heterocyclizations,
various
oxidative
functionalizations
of
substrates.
Iodonium
salts
arylating
reagents,
while
iodonium
ylides
imides
excellent
carbene
nitrene
precursors.
Various
derivatives
benziodoxoles,
such
azidobenziodoxoles,
trifluoromethylbenziodoxoles,
alkynylbenziodoxoles,
alkenylbenziodoxoles
group
transfer
the
presence
transition
metal
catalysts,
under
metal-free
conditions,
or
using
photocatalysts
photoirradiation
conditions.
Development
hypervalent
catalytic
systems
discovery
highly
enantioselective
reactions
chiral
represent
a
particularly
recent
achievement
field
chemistry.
Chemical
transformations
promoted
by
many
cases
unique
cannot
be
performed
any
other
common,
non-iodine-based
reagent.
This
review
covers
literature
published
mainly
last
7-8
years,
between
2016
2024.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(9), С. 4975 - 4981
Опубликована: Фев. 22, 2023
We
describe
the
first
catalytic
generation
of
Fischer-type
acyloxy
Rh(II)-carbenes
from
carboxylic
acids
and
Rh(II)-carbynoids.
This
novel
class
transient
donor/acceptor
evolved
through
a
cyclopropanation
process
providing
access
to
densely
functionalized
cyclopropyl-fused
lactones
with
excellent
diastereoselectivity.
DFT
calculations
allowed
analysis
properties
Rh(II)-carbynoids
as
well
characterization
mechanism.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(16), С. 2653 - 2675
Опубликована: Апрель 21, 2023
Abstract
Hypervalent
iodine
compounds
have
found
broad
application
in
modern
organic
chemistry
as
reagents
and
catalysts.
Cyclic
hypervalent
based
on
the
benziodoxole
heterocyclic
system
higher
stability
compared
to
their
acyclic
analogues,
which
makes
possible
preparation
safe
handling
of
with
special
ligands
such
azido,
cyano,
trifluoromethyl
groups.
Numerous
iodine‐substituted
derivatives
been
prepared
utilized
for
transfer
substituent
substrate.
Reactions
these
substrates
can
be
performed
under
metal‐free
conditions,
presence
transition
metal
catalysts,
or
using
photocatalysts
photoirradiation
conditions.
In
this
review,
we
focus
most
recent
synthetic
applications
cyclic
iodine(III)
following
ligands:
N
3
,
NHR,
CN,
CF
SCF
OR,
OAc,
ONO
2
C(=N
)CO
R.
The
review
covers
literature
published
mainly
last
5
years.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(48), С. 26403 - 26411
Опубликована: Ноя. 22, 2023
Multifunctionalization
from
the
interception
of
active
intermediates
is
an
attractive
synthetic
strategy
for
efficient
construction
complex
molecular
scaffolds
in
atom
and
step
economic
fashion.
However,
design
reactions
involving
metal
carbynoids
that
exhibit
carbene/carbocation
behavior
currently
limited,
developing
catalyst-controlled
highly
enantioselective
versions
poses
significant
challenges.
In
this
study,
we
present
first
asymmetric
trifunctionalization
with
rhodium
carbynoids.
This
reaction
unveils
distinctive
reactivity
carbynoid
precursor,
enabling
it
to
react
simultaneously
two
nucleophiles
one
electrophile.
process
involves
formation
distinct
carbene
ylides
alcohol/carbamate
trapping
ylide
imine,
resulting
three
new
bonds.
Furthermore,
allows
divergent
synthesis
a
wide
array
β-amino
esters
high
yields
exceptional
enantioselectivity.
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.
Nature Chemistry,
Год журнала:
2024,
Номер
16(6), С. 901 - 912
Опубликована: Май 23, 2024
Abstract
Cyclopropenes
are
the
smallest
unsaturated
carbocycles.
Removing
one
substituent
from
cyclopropenes
leads
to
cyclopropenium
cations
(C
3
+
systems,
CPCs).
Stable
aromatic
π
-type
CPCs
were
discovered
by
Breslow
in
1957
removing
a
on
aliphatic
position.
In
contrast,
σ
CPCs—formally
accessed
alkene—are
unstable
and
relatively
unexplored.
Here
we
introduce
electrophilic
cyclopropenyl-gold(III)
species
as
equivalents
of
CPCs,
which
can
then
react
with
terminal
alkynes
vinylboronic
acids.
With
catalyst
loadings
low
2
mol%,
synthesis
highly
functionalized
alkynyl-
or
alkenyl-cyclopropenes
proceeded
under
mild
conditions.
A
class
hypervalent
iodine
reagents—the
cyclopropenyl
benziodoxoles
(CpBXs)—enabled
direct
oxidation
gold(I)
gold(III)
concomitant
transfer
group.
This
protocol
was
general,
tolerant
numerous
functional
groups
could
be
used
for
late-stage
modification
complex
natural
products,
bioactive
molecules
pharmaceuticals.
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.
Chemical Society Reviews,
Год журнала:
2024,
Номер
53(9), С. 4786 - 4827
Опубликована: Янв. 1, 2024
This
review
summarizes
structural
and
synthetic
aspects
of
heterocyclic
molecules
incorporating
an
atom
a
hypervalent
main-group
element.
The
higher
thermal
stability
heterocycles,
as
compared
to
their
acyclic
analogs,
adds
special
feature
chemistry.
