Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(45)
Опубликована: Сен. 19, 2023
Abstract
Insertion
reactions
that
involve
stabilized
electrophilic
metallocarbenes
are
of
great
importance
for
installing
α‐heteroatoms
to
carbonyl
compounds.
Nevertheless,
the
limited
availability
carbene
precursors
restricts
introduction
only
a
single
heteroatom.
In
this
report,
we
describe
new
approach
based
on
an
I
(III)
/S
(VI)
reagent
promotes
cascade
insertion
heteroatoms.
This
is
achieved
by
sequentially
generating
two
α‐heteroatom‐substituted
metal
carbenes
in
one
reaction.
We
found
mixed
ylide
reacts
efficiently
with
transition
catalyst
and
X−H
bond
(where
X=O,
N).
transformation
leads
sequential
formation
sulfoxonium‐
X‐substituted
Rh‐carbenes,
enabling
further
another
Y−H
bond.
Remarkably,
wide
range
symmetrical
unsymmetrical
α,α‐
O
,
‐,
N
‐subsituted
ketones
can
be
prepared
under
mild
ambient
conditions.
addition,
successfully
demonstrated
other
cascades,
such
as
CN/CN
double
amidation,
C−H/C−S
insertion,
C−S/Y−H
Y=S,
N,
O,
C).
Notably,
latter
cascades
enabled
simultaneous
installation
three
functional
groups
α‐carbon
compounds
step.
These
demonstrate
versatility
our
approach,
allowing
synthesis
esters
multiple
using
common
precursor.
Advanced Synthesis & Catalysis,
Год журнала:
2020,
Номер
363(4), С. 877 - 905
Опубликована: Дек. 19, 2020
Abstract
The
use
of
diazo
compounds
in
the
transition‐metal‐catalyzed
coupling
reactions
to
form
C−C
and
C−X
(X=O,
S,
N,
Si,
P
etc.)
bonds
have
been
a
well
established
approach
organic
synthesis.
In
this
context,
various
transition
metals
such
as
Pd,
Cu,
Rh,
Ni,
Co,
Fe,
Ir
etc.
proved
useful
generate
metal‐carbene
intermediate
which
subsequently
undergoes
carbene
transfer
or
insertion
C−C,
C−Si
C‐heteroatom
bonds.
However,
most
abundant,
cheaper
environmentally
benign
metal
iron
catalyze
carbene‐transfer
has
attracted
considerable
attention
last
few
years.
Iron
is
second
abundant
nature
also
an
integral
part
biological
systems
make
it
highly
valuable
catalyst
chemistry.
This
review
summarizes
efforts
made
after
2013
area
iron‐catalyzed
chemical
enzymatic
using
precursor.
magnified
image
Organic & Biomolecular Chemistry,
Год журнала:
2022,
Номер
21(1), С. 24 - 38
Опубликована: Ноя. 23, 2022
The
metal-catalyzed
successive
activation
and
functionalization
of
arene/heteroarene
is
one
the
most
fundamental
transformations
in
organic
synthesis
leads
to
privileged
scaffolds
natural
products,
pharmaceuticals,
agrochemicals,
fine
chemicals.
Particularly,
transition-metal-catalyzed
C-H
arenes
with
carbene
precursors
via
metal
migratory
insertion
has
been
well
studied.
As
a
result,
diverse
have
evaluated,
such
as
diazo
compounds,
sulfoxonium
ylides,
triazoles,
etc.
In
addition,
there
significant
developments
use
iodonium
ylides
recent
years,
these
reactions
proceed
high
efficiencies
selectivities.
This
review
provides
comprehensive
overview
functionalizations,
including
scope,
limitations,
their
potential
synthetic
applications.
RSC Advances,
Год журнала:
2022,
Номер
12(23), С. 14435 - 14438
Опубликована: Янв. 1, 2022
A
redox-neutral
synthesis
of
dibenzo[b,d]pyran-6-ones
from
aryl
ketone
O-acetyl
oximes
and
quinones
has
been
realized
via
Rh(iii)-catalyzed
cascade
C-H
activation
annulation.
possible
Rh(iii)-Rh(v)-Rh(iii)
mechanism
involving
an
unprecedented
β-C
elimination
step
was
proposed.
Organic Letters,
Год журнала:
2022,
Номер
24(25), С. 4536 - 4541
Опубликована: Июнь 23, 2022
A
weakly
coordinating
tert-amide-directed
straightforward
method
was
developed
for
the
synthesis
of
azacoumestans
using
corresponding
azaheterocycle
derivatives
and
diazonaphthoquinones
under
cheap
Ru(II)-catalyzed
conditions.
The
reaction
proceeds
via
migratory
insertion
quinoid
carbene
subsequent
Brønstead
acid-mediated
cyclization.
optimized
C2-selective
offered
a
wide
scope
important
azaheterocycles.
Bioactive
natural
products
like
isolamellarins
B
were
synthesized
protocol.
Preliminary
mechanistic
studies
highlighted
probable
pathway.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(45)
Опубликована: Сен. 19, 2023
Abstract
Insertion
reactions
that
involve
stabilized
electrophilic
metallocarbenes
are
of
great
importance
for
installing
α‐heteroatoms
to
carbonyl
compounds.
Nevertheless,
the
limited
availability
carbene
precursors
restricts
introduction
only
a
single
heteroatom.
In
this
report,
we
describe
new
approach
based
on
an
I
(III)
/S
(VI)
reagent
promotes
cascade
insertion
heteroatoms.
This
is
achieved
by
sequentially
generating
two
α‐heteroatom‐substituted
metal
carbenes
in
one
reaction.
We
found
mixed
ylide
reacts
efficiently
with
transition
catalyst
and
X−H
bond
(where
X=O,
N).
transformation
leads
sequential
formation
sulfoxonium‐
X‐substituted
Rh‐carbenes,
enabling
further
another
Y−H
bond.
Remarkably,
wide
range
symmetrical
unsymmetrical
α,α‐
O
,
‐,
N
‐subsituted
ketones
can
be
prepared
under
mild
ambient
conditions.
addition,
successfully
demonstrated
other
cascades,
such
as
CN/CN
double
amidation,
C−H/C−S
insertion,
C−S/Y−H
Y=S,
N,
O,
C).
Notably,
latter
cascades
enabled
simultaneous
installation
three
functional
groups
α‐carbon
compounds
step.
These
demonstrate
versatility
our
approach,
allowing
synthesis
esters
multiple
using
common
precursor.
