The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(11), С. 7392 - 7404
Опубликована: Май 20, 2022
In
this
paper,
an
efficient
synthesis
of
N-arylindoles
through
the
cascade
reaction
2-alkenylanilines
with
diazonaphthalen-2(1H)-ones
is
presented.
Mechanistically,
involves
generation
a
Ru-carbene
complex
from
diazonaphthalen-2(1H)-one,
followed
by
carbene
N-H
bond
insertion
2-alkenylaniline,
intramolecular
cyclization,
and
oxidative
aromatization.
reaction,
Ru(II)
acts
as
multifunctional
catalyst
to
promote
not
only
formation
but
also
cyclization
dehydrogenative
Meanwhile,
air
green
cost-effective
oxidant.
To
our
knowledge,
first
example
in
which
were
synthesized
simultaneous
introduction
N-aryl
unit
construction
indole
scaffold.
Notable
advantages
method
include
readily
accessible
halide-free
substrates,
additive-free
conditions,
good
efficiency,
excellent
atom
economy,
compatibility
diverse
functional
groups.
addition,
utility
product
thus
obtained
was
showcased
its
structural
transformations.
Chemical Reviews,
Год журнала:
2017,
Номер
117(23), С. 13810 - 13889
Опубликована: Ноя. 1, 2017
Transition-metal-catalyzed
cross-coupling
reactions
have
been
well-established
as
indispensable
tools
in
modern
organic
synthesis.
One
of
the
major
research
goals
area
is
expanding
scope
coupling
partners.
In
past
decade,
diazo
compounds
(or
their
precursors
N-tosylhydrazones)
emerged
nucleophilic
partners
C-C
single
bond
or
C═C
double
formations
transition-metal-catalyzed
reactions.
This
type
reaction
involves
following
general
steps.
First,
organometallic
species
generated
by
various
processes,
including
oxidative
addition,
transmetalation,
cyclization,
cleavage,
and
C-H
activation.
Subsequently,
reacts
with
substrate
to
generate
metal
carbene
intermediate,
which
undergoes
rapid
migratory
insertion
form
a
bond.
The
new
from
may
undergo
transformations.
carbene-based
has
proven
be
general:
transition
metals
Pd,
Cu,
Rh,
Ni,
Co,
Ir
are
effective
catalysts;
also
extended
substrates
other
than
compounds;
cascade
processes
devised
based
on
insertion.
review
will
summarize
achievements
made
this
field
since
2001.
Advanced Synthesis & Catalysis,
Год журнала:
2018,
Номер
361(5), С. 919 - 944
Опубликована: Ноя. 27, 2018
Abstract
This
review
covers
some
unique
diazo
compounds,
the
coupling
partners
to
access
various
versatile
functionalized
nitrogen
heterocycles,
such
as
indoles,
indolines,
isoquinolines,
isoquinolones,
and
so
on.
Different
transition
metals
(such
Rh,
Pd,
Ru,
Ir,
Cu,
Co)
are
involved
in
these
transformations,
which
involve
consecutive
processes:
metal‐catalyzed
cascade
C–H
activation/carbene
insertion/intramolecular
annulation.
magnified
image
Organic Letters,
Год журнала:
2019,
Номер
21(8), С. 2541 - 2545
Опубликована: Апрель 8, 2019
An
unprecedented
cascade
reaction
of
benzoyl
sulfoxonium
ylides
with
α-diazocarbonyl
compounds
leading
to
the
formation
highly
functionalized
naphthalenones
containing
a
β-ketosulfoxonium
ylide
moiety
is
presented.
Promisingly,
naphthalenone
derivative
thus
obtained
was
found
be
versatile
intermediate
toward
diversely
naphthalene
derivatives
including
substituted
1-naphthol,
2-hydroxynaphthalen-1(2H)-one,
naphthalen-1,2-dione,
and
2-(methylsulfinyl)naphthalen-1-ol.
Advanced Synthesis & Catalysis,
Год журнала:
2018,
Номер
360(19), С. 3781 - 3787
Опубликована: Июль 12, 2018
Abstract
A
highly
chem‐
and
regioselective
synthesis
of
diversely
substituted
benzo[
a
]carbazoles
indolo[2,1‐
]‐isoquinolines
through
Rh(III)‐catalyzed
cascade
reactions
2‐arylindoles
with
sulfoxonium
ylides
is
presented.
To
be
specific,
treatment
2‐arylindoles,
2‐arylindole‐3‐carbaldehydes,
2‐arylindole‐3‐carbonitriles
or
2‐aryl‐3‐methylindoles
under
the
catalysis
Rh(III)
led
to
selective
formation
6‐aryl/alkyl
]carbazoles,
5‐acylbenzo[
6‐amino‐5‐acylbenzo[
12‐methylindolo[2,1‐
]isoquinolines,
respectively.
Mechanistically,
title
compounds
involves
process
including
metalation
inert
C(
sp
2
)−H
bond,
migratory
insertion
ylide
into
carbon‐metal
bond
via
an
in
situ
carbenoid
formation,
protodemetalation,
condensation.
our
knowledge,
this
first
example
which
β‐carbonyl
were
used
as
stable
carbene
precursors
bifunctional
C2
synthons
afford
]isoquinolines.
magnified
image
ACS Catalysis,
Год журнала:
2020,
Номер
10(17), С. 9747 - 9757
Опубликована: Авг. 3, 2020
Transition-metal-catalyzed
C–H
activation
followed
by
oxidative
cyclization
with
unsaturated
coupling
partners
has
been
a
valuable
synthetic
tool
for
the
multiring
molecular
scaffolds.
This
Perspective
introduces
recent
progress
on
Cp*M-catalyzed
(M
=
Co,
Rh,
and
Ir)
direct
annulation
of
functionalized
arenes
terminal
alkynes
their
equivalents
through
bond
cleavage.
The
highlighted
examples
are
categorized
according
to
10
different
types
reagents
used
in
transformations.
representative
conditions,
selected
reaction
scope,
key
mechanistic
aspects
briefly
summarized.
Organic Letters,
Год журнала:
2019,
Номер
21(18), С. 7189 - 7193
Опубликована: Сен. 4, 2019
A
dehydrogenative
annulation
of
2-arylindazoles
with
maleimides
for
the
switchable
synthesis
indazolo[2,3-a]pyrrolo[3,4-c]quinolinones
or
spiroindolo[1,2-b]indazole-11,3′-pyrrolidinones
is
presented.
Mechanistically,
formation
title
compounds
involves
a
Rh(III)-catalyzed
C–H
metalation
2-arylindazole,
followed
by
maleimide
insertion
and
intramolecular
cyclization.
Interestingly,
selectivity
to
form
fused
spiro
could
be
switched
resorting
different
additives.
The
notable
features
this
protocol
include
simple
substrates
excellent
atom
economy
regioselectivity.
Organic Chemistry Frontiers,
Год журнала:
2021,
Номер
8(11), С. 2710 - 2771
Опубликована: Янв. 1, 2021
This
review
presents
a
critical
and
authoritative
analysis
of
several
exciting
benzannulation
approaches
developed
in
the
past
decade
for
construction
carbazoles,
indolocarbazoles,
benzocarbazoles,
carbolines.
Organic Letters,
Год журнала:
2022,
Номер
24(6), С. 1280 - 1285
Опубликована: Фев. 7, 2022
Synthesis
of
spiro[benzo[d][1,3]oxazine-4,4'-isoquinoline]s
through
a
unique
[4+1+1]
annulation
N-aryl
amidines
with
diazo
homophthalimides
and
O2
is
presented.
This
unprecedented
spirocyclization
reaction
features
readily
obtainable
substrates,
structurally
pharmaceutically
attractive
products,
cost-free
clean
oxygen
source,
sustainable
medium,
tolerance
broad
spectrum
functional
groups,
an
interesting
mechanism
based
on
sequential
C(sp2)-H/C(sp3)-H
bond
cleavage
insertion.
Advanced Synthesis & Catalysis,
Год журнала:
2018,
Номер
360(18), С. 3534 - 3543
Опубликована: Июль 3, 2018
Abstract
A
Ru(II)‐catalyzed
approach
for
the
rapid
assembly
of
1,2‐benzothiazines
has
been
developed
to
enable
coupling‐cyclization
aryl
C
sp
2
−H
bonds
with
α‐carbonyl
sulfoxonium
ylides
via
activation
process.
The
present
method
could
be
further
applied
construction
4‐substituted
1,2‐benzothiazine
skeletons.
magnified
image
Organic Letters,
Год журнала:
2017,
Номер
19(9), С. 2294 - 2297
Опубликована: Апрель 24, 2017
An
unprecedented
Rh(III)-catalyzed
double
C(sp2)–H
bond
carbenoid
insertion
and
annulation
of
2-aryl-3-cyanopyridines
with
α-diazo
carbonyl
compounds
is
presented.
Through
this
cascade
reaction,
a
series
naphthoquinolizinone
derivatives
large
π-system
were
efficiently
prepared.
The
reactions
could
selectively
afford
naphthoquinolizinones
either
an
amine
or
amide
unit
attached
on
the
11-position
depending
nature
solvent
additive
used.
Compared
literature
methods,
more
efficient,
convenient,
atom-economic
way
to
provide
polycyclic
heteroaromatic
through
direct
π-extension
simple
aromatics
via
inert
C–H
activation
functionalization.
