Chemical Communications,
Journal Year:
2019,
Volume and Issue:
55(74), P. 11111 - 11114
Published: Jan. 1, 2019
A
new,
general
silver-catalyzed
oxidative
1,2-alkyletherification
of
unactivated
olefinic
ketones
with
primary,
secondary
and
tertiary
α-bromoalkyl
carbonyls
promoted
by
tert-butyl
hydroperoxide
(TBHP)
Et3N
has
been
developed.
Through
the
cooperative
action
Ag2O,
TBHP
Et3N,
reaction
enables
construction
highly
valuable
quaternary-carbon-possessing
2,3-dihydrofuran
frameworks
using
a
concomitant
intramolecular
annulation
strategy.
Chemical Reviews,
Journal Year:
2019,
Volume and Issue:
119(20), P. 11110 - 11244
Published: Sept. 6, 2019
This
review
article
will
consider
the
preparation
and
application
of
ynones
in
synthetic
organic
chemistry.
Concerning
these
bifunctional
compounds,
several
methodologies
starting
from
propargyl
alcohols,
acyl
derivatives,
both
by
using
alkynylmetal
reagents
or
transition
metal
(mainly
palladium
copper)
catalyzed
alkynylations,
carbon
monoxide
(carbonylation
terminal
alkynes
alkenes),
other
substrates
be
discussed.
The
reactivity
applications
focused
on
conjugate
additions
with
boron-,
carbon-,
nitrogen-,
oxygen-,
heteroatom-containing
nucleophiles,
as
well
radicals.
Then,
cycloaddition
processes
include
[2
+
2]
cycloadditions,
[3
1,3-dipolar
cycloadditions
(with
azides,
nitrones,
azomethine
imines
ylides,
nitrile
oxides,
diazo
dipoles),
[4
Diels-Alder-type
reactions).
reduction
triple
bond,
addition
to
carbonyl
group
(using
carbon-
heteronucleophiles
reductions),
not
so
commonly
used
(such
aldol
reactions,
cyclizations,
isomerizations)
considered
at
end.
Chemical Science,
Journal Year:
2019,
Volume and Issue:
11(5), P. 1353 - 1360
Published: Dec. 13, 2019
Indole-tethered
ynones
form
an
intramolecular
electron
donor–acceptor
complex
that
can
undergo
visible-light-induced
charge
transfer
to
promote
thiyl
radical
generation
from
thiols.
This
initiates
a
novel
chain
sequence,
based
on
dearomatising
spirocyclisation
with
concomitant
C–S
bond
formation.
Sulfur-containing
spirocycles
are
formed
in
high
yields
using
this
simple
and
mild
synthetic
protocol,
which
neither
transition
metal
catalysts
nor
photocatalysts
required.
The
proposed
mechanism
is
supported
by
various
mechanistic
studies,
the
unusual
initiation
mode
represents
only
second
report
of
use
synthesis.
Asian Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
12(6)
Published: May 2, 2023
Abstract
The
derivatives
of
indoles
are
very
useful
intermediates
in
pharmaceuticals
and
organic
synthesis.
efficient
synthesis
the
indole
blocks
related
functionalizations,
especially
alkylation
hot
topics
recent
years.
This
review
will
focus
on
following
two
aspects:
i)
new
developments
for
which
was
catalyzed
by
transition
metals,
indoles,
including
one
N
1
‐position,
C
2
as
well
3
‐position.
1.
Introduction
2.
Synthesis
various
metals
2.1.
palladium
catalysts
2.2.
other
metal
3.
Alkylation
3.1.
‐alkylation
3.2.
3.3.
ACS Catalysis,
Journal Year:
2018,
Volume and Issue:
9(1), P. 504 - 510
Published: Dec. 4, 2018
A
one-pot
protocol
for
the
dearomatizing
spirocyclization/cross-coupling
of
alkyne-tethered
indoles/pyrroles
is
described.
Mechanistic
studies
support
a
process
by
which
palladium
complexes
generated
in
situ
act
as
both
π-acid
and
cross-coupling
catalysts.
Overall,
this
facilitates
an
efficient
cascade
that
enables
simultaneous
preparation
synthetically
challenging
quaternary
spirocyclic
carbons
tetrasubstituted
alkenes
single
operation.
ChemCatChem,
Journal Year:
2020,
Volume and Issue:
12(20), P. 5034 - 5050
Published: July 24, 2020
Abstract
Silver,
as
one
of
the
most
ancient
coinage
metals,
has
attracted
a
plethora
attention
from
chemists
in
recent
years
due
to
easy
availability,
high
catalytic
efficiency
and
multiple
functions
displayed
various
chemical
processes.
In
particular,
research
this
field
gained
great
progress
since
2007
several
elegant
reviews
have
been
documented
literature.
However,
there
no
systematic
review
concentrating
on
transformations
electronically
unbiased
alkenes
alkynes
under
silver
catalysis
till
now,
though
rapid
development
area
is
witnessed.
Therefore,
mainly
focuses
advances
silver‐catalyzed
reactions
different
electron‐unbiased
alkynes,
covering
examples
hydrofunctionalization
reactions,
difunctionalization
cross‐coupling
well
cyclization
2015
February
2020.
addition,
some
interesting
mechanisms
were
also
discussed.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(2), P. 668 - 674
Published: Jan. 5, 2022
Indole-ynones
have
been
established
as
general
substrates
for
radical
dearomatizing
spirocyclization
cascade
reactions.
Five
distinct
and
varied
synthetic
protocols
developed─cyanomethylation,
sulfonylation,
trifluoromethylation,
stannylation
borylation─using
a
variety
of
generation
modes,
ranging
from
photoredox
catalysis
to
traditional
AIBN
methods.
The
simple
easily
prepared
indole-ynones
can
be
used
rapidly
generate
diverse,
densely
functionalized
spirocycles
the
potential
become
routinely
explore
reactivity.
Experimental
computational
investigations
support
proposed
mechanism
suggest
that
other
new
methods
are
now
primed
development.
Tetrahedron Chem,
Journal Year:
2024,
Volume and Issue:
9, P. 100055 - 100055
Published: Jan. 14, 2024
This
review
concentrates
on
our
research
into
the
discovery
of
novel
ynone-based
dearomative
spirocyclisation
processes,
whilst
placing
new
chemistry
context
existing
knowledge.
The
genesis
programme,
development
efficient
synthetic
routes
to
prepare
natural
products
spirobacillene
A
(1)
and
B
(2),
utilised
indole
ynones.
stimulated
a
much
wider
study
explore
reactivity
ynones
in
processes
more
generally.
Routes
generate
wide
range
spirocycles
were
subsequently
developed,
with
reactions
tethered
indoles,
benzofurans,
benzisoxazoles,
pyrroles,
pyridines,
isoquinolines,
pyrazines,
cyclic
ketimines,
anisoles
all
discussed
herein,
these
initiated
by
catalytic
Ag(I),
Cu(II),
Pd(0),
photolysis
many
other
reagents.
Asymmetric
variants
some
are
also
discussed,
as
is
further
elaboration
spirocyclic
give
carbazoles,
quinolones,
polycycles
useful
building
blocks.
Finally,
applications
methodology
product
synthesis
(e.g.
A,
lasubine
II
indolizidine
209D)
described.
Chemistry - An Asian Journal,
Journal Year:
2019,
Volume and Issue:
14(11), P. 1900 - 1911
Published: March 25, 2019
Abstract
Indoles
are
amongst
the
most
important
classes
of
heteroaromatics
in
organic
chemistry,
commonly
found
biologically
active
natural
products
and
therapeutically
useful
compounds.
The
synthesis
indoles
is
therefore
several
methods
for
their
that
make
use
silver(I)
catalysts
reagents
have
been
developed
recent
years.
This
Minireview
contains,
to
best
our
knowledge,
a
comprehensive
coverage
silver‐mediated
indole
forming
reactions
since
first
reaction
this
type
was
reported
2004.
Organic & Biomolecular Chemistry,
Journal Year:
2022,
Volume and Issue:
20(15), P. 3029 - 3042
Published: Jan. 1, 2022
Indoles
are
one
of
the
most
prominent
aromatic
heterocycles
in
organic
chemistry
field.
Due
to
their
widespread
presence
various
natural
products,
alkaloids,
drugs,
approved
medicines,
etc.
synthesis
and
functionalization
indoles
great
interest.
This
review
emphasizes
recent
developments
techniques
domino
cascade
cyclization
process
last
decade
starting
from
building
blocks.
In
particular,
this
depicts
several
intriguing
benzannulation
methods
creating
a
benzene
ring
on
pre-existing
pyrrole
nucleus
an
inter/intramolecular
fashion
under
metal-catalyzed/metal-free
approaches.
Different
subsections
focus
gradual
timely
complementary
area
detailed
analysis
mechanisms
reactivity
patterns.
As
method,
gives
significant
incentive
annulation
strategies
also
overview
remaining
challenges
upcoming
possibilities.
