Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(10)
Published: Jan. 14, 2023
Abstract
[2,3]‐Sigmatropic
rearrangement
reaction
involving
sulfonium
ylide
(Doyle–Kirmse
reaction)
generated
from
metal
carbenes
represents
one
of
the
powerful
methods
for
construction
C(sp
3
)−S
and
C−C
bonds.
Although
significant
advances
have
been
achieved,
asymmetric
versions
via
generation
ylides
rarely
reported
to
date,
they
so
far
limited
diazo
compounds
as
carbene
precursors.
Here,
we
describe
a
copper‐catalyzed
enantioselective
Doyle–Kirmse
azide‐ynamide
cyclization,
leading
practical
divergent
assembly
an
array
chiral
[1,4]thiazino[3,2‐
b
]indoles
bearing
quaternary
carbon
stereocenter
in
generally
moderate
excellent
yields
enantioselectivities.
Importantly,
this
protocol
unique
catalytic
non‐diazo
approach
unprecedented
[2,3]‐sigmatropic
α‐imino
carbenes.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(10)
Published: Jan. 14, 2023
[2,3]-Sigmatropic
rearrangement
reaction
involving
sulfonium
ylide
(Doyle-Kirmse
reaction)
generated
from
metal
carbenes
represents
one
of
the
powerful
methods
for
construction
C(sp3
)-S
and
C-C
bonds.
Although
significant
advances
have
been
achieved,
asymmetric
versions
via
generation
ylides
rarely
reported
to
date,
they
so
far
limited
diazo
compounds
as
carbene
precursors.
Here,
we
describe
a
copper-catalyzed
enantioselective
Doyle-Kirmse
azide-ynamide
cyclization,
leading
practical
divergent
assembly
an
array
chiral
[1,4]thiazino[3,2-b]indoles
bearing
quaternary
carbon
stereocenter
in
generally
moderate
excellent
yields
enantioselectivities.
Importantly,
this
protocol
unique
catalytic
non-diazo
approach
unprecedented
[2,3]-sigmatropic
α-imino
carbenes.
Asian Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
12(8)
Published: June 21, 2023
Abstract
Indole
heterocycles
hold
an
important
position
in
chemical
landscape
because
of
their
prominence
natural
products
and
pharmaceuticals.
Consequently,
development
new
efficient
strategies
to
access
indole
scaffold
are
continuous
interest.
For
the
past
few
years,
gold‐catalyzed
activation
alkyne
has
emerged
as
a
powerful
strategy
for
constructing
heterocyclic
skeleton.
The
present
review
highlights
recent
advances
(2018–2023)
toward
synthesis
skeletons
via
annulations
alkynes.
A
variety
alkynes,
such
as,
ynamides,
azido
ortho
‐alkynyl
anilines,
propargylic
alcohols,
phenylimines,
miscellaneous
alkynes
employed
affording
various
architectures
under
gold
catalysis.
Moreover,
mechanisms
included
most
cases
better
understanding
reaction
pathway.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(22), P. 3855 - 3860
Published: Oct. 18, 2023
Abstract
A
rhodium(III)‐catalyzed
C−H
activation/[4+1]
annulation
of
2‐aryl‐3
H
‐indoles
and
CF
3
‐substituted
imidoyl
sulfoxonium
ylides
(TFISYs)
has
been
achieved,
producing
a
wide
variety
trifluoroacetimidoyl‐substituted
11
‐isoindolo[2,1‐a]indoles
in
51–86%
yields.
The
cascade
reaction
involves
imidoylmethylation,
tautomerization
AgOAc‐mediated
C−N
bond
formation
sequence.
could
be
scaled
up
to
2
mmol
scale.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(26)
Published: April 27, 2023
Selective
functionalization
of
non-activated
C(sp3
)-H
bonds
is
a
major
challenge
in
chemistry,
so
functional
groups
are
often
used
to
enhance
reactivity.
Here,
we
present
gold(I)-catalyzed
activation
1-bromoalkynes
without
any
sort
electronic,
or
conformational
bias.
The
reaction
proceeds
regiospecifically
and
stereospecifically
the
corresponding
bromocyclopentene
derivatives.
latter
can
be
readily
modified,
comprising
an
excellent
library
diverse
3D
scaffolds
for
medicinal
chemistry.
In
addition,
mechanistic
study
has
shown
that
via
far
unknown
mechanism:
concerted
[1,5]-H
shift
/
C-C
bond
formation
involving
gold-stabilized
vinylcation-like
transition
state.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(3), P. 631 - 635
Published: Jan. 12, 2024
A
gold-catalyzed,
nucleophile-controlled
cascade
reaction
of
N-(2-azidophenyl-ynyl)methanesulfonamides
with
nitriles
and
water
is
described
that
provides
structurally
diverse
5H-pyrimido[5,4-b]indoles
2-benzylidene-3-indolinones
in
good
to
excellent
yields.
Mechanistic
studies
indicate
the
β-sulfonamido-α-imino
gold
carbene
key
intermediate
which
generated
through
gold-catalyzed
cyclization
undergoes
formal
[4
+
2]
annulation
intramolecular
SN2′
type
water,
respectively.
Chemical Society Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
This
review
summarizes
the
latest
trends
and
developments
of
isoxazole-enabled
alkyne
amination
reactions
their
applications
in
divergent
heterocycle
synthesis.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(2), P. 421 - 425
Published: Jan. 9, 2023
α-(3-Indolyl)ketones
are
essential
building
blocks
for
the
generation
of
biologically
active
molecules.
We
described
a
new
method
direct
assembly
α-(3-indolyl)ketones
through
cascade
reaction
2-alkynyl
aryl
azides
with
enecarbamates,
in
which
situ
generated
α-imino
gold
carbene
intermediate
was
trapped
by
enecarbamate
to
achieve
umpolung
reactivity
indole
at
3-position.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(7), P. 4391 - 4397
Published: March 16, 2023
Reported
herein
is
the
fluorination
of
α-imino
gold
carbenes,
generated
in
situ
from
azidoalkynes,
to
access
substituted
C3-fluorinated
quinolones
and
indoles.
The
methodology
has
been
applied
for
synthesizing
quinolone-
quinoline-based
natural
products,
including
pseudanes
(4
representative
examples),
chimanine
A,
graveolinine.
Mechanistic
investigations,
NMR
SC-XRD
analysis,
reveal
that
NEt3·3HF
reacts
with
catalyst
generate
a
phosphine-ligated
fluoride-bridged
binuclear
complex
which
then
generates
active
this
reaction.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(12), P. 2063 - 2067
Published: March 20, 2023
A
novel
copper-catalyzed
tandem
cyclization/direct
C(sp2)–H
annulation
of
phenyl
azide–ynamides
via
α-imino
copper
carbenes
has
been
developed,
which
provides
a
concise
and
flexible
approach
for
the
construction
range
valuable
azepino[2,3-b:4,5-b′]diindoles
in
mostly
good
to
excellent
yields
with
high
chemoselectivities.
This
reaction
also
exhibits
broad
substrate
scope,
functional
group
tolerance,
simple
operation,
mild
conditions.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(10), P. 1623 - 1628
Published: May 5, 2023
Abstract
A
rhodium‐catalyzed
cascade
1,3‐sulfinate
migration,
intermolecular
[3+2]
annulation
of
1‐sulfonyl‐1,2,3‐triazoles
and
indoles
was
achieved.
The
one‐pot
protocol
provided
a
method
to
construct
cyclopenta[
b
]indoles
bearing
four
stereocenters
in
45%
99%
yields
with
1.6:1
>20:1
diastereoselectivities.
In
addition,
could
be
transformed
into
variety
functionalized
compounds,
demonstrating
the
synthetic
value
this
migration‐annulation
strategy
ring
system
synthesis.
magnified
image
