Beilstein Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
19, P. 1966 - 1981
Published: Dec. 28, 2023
In
order
to
replace
the
expensive
metal/ligand
catalysts
and
classic
toxic
volatile
solvents,
commonly
used
for
hydration
of
alkynes,
reaction
alkynes
was
studied
in
ionic
liquid
1-butyl-3-methylimidazolium
tetrafluoroborate
(BMIm-BF
4
)
adding
boron
trifluoride
diethyl
etherate
(BF
3
·Et
2
O)
as
catalyst.
Different
liquids
were
used,
varying
cation
or
anion,
identify
best
one,
terms
both
efficiency
reduced
costs.
The
developed
method
efficaciously
applied
different
achieving
desired
products
with
good
yields.
results
obtained
using
a
conventional
approach
(i.e.,
BF
compared
those
achieved
electrogenerated
BMIm-BF
,
demonstrating
possibility
obtaining
alkyne
analogous
improved
yields,
less
hazardous
precursors
generate
reactive
species
situ.
particular,
terminal
arylalkynes,
electrochemical
route
proved
be
advantageous,
yielding
preferentially
vs
aldol
condensation
products.
Importantly,
ability
recycle
subsequent
reactions
successfully
demonstrated.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(11), P. 1770 - 1776
Published: March 21, 2023
Abstract
Rh‐catalyzed
C−H
activation
of
arenes
for
oxidative
annulations
with
alkynes
stands
out
as
a
protocol
polycyclic
scaffolds.
This
perspective
drives
us
to
disclose
herein
rhodium
catalyzed
regioselective
triple
annulation
enaminones
hydroxyl‐alkynoates
via
double
functionalization
naphtho‐pyran
Secondary
coordination
OH
in
alkynoate
dictated
the
regioselectivity.
Initial
lactonization
occurred
chemoselectively
on
enamine
part
carbo
rhodation
followed
by
reductive
elimination.
was
scalable
and
has
shown
high
functionality
tolerance.
KIE
studies
were
done
get
insight
mechanism,
some
downstream
transformations
achieved
show
synthetic
potential
method.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(64), P. 9714 - 9717
Published: Jan. 1, 2023
A
Pd-catalyzed
rollover
cascade
dual
C–H
annulation
of
aryl
phenols
with
alkynols
for
producing
phenanthrene
scaffolds
in
a
regioselective
manner
was
developed.
Necessary
control,
KIE
and
deuterium
experiments
were
conducted
to
determine
the
reaction
mechanism.
ChemistrySelect,
Journal Year:
2025,
Volume and Issue:
10(2)
Published: Jan. 1, 2025
Abstract
Isoquinoline
is
a
privileged
structural
motif
and
has
extensive
applications
in
asymmetric
catalysis,
photochemistry,
pharmaceutical
use.
Naturally,
isoquinoline
popular
synthetic
target
for
many
research
groups
worldwide,
who,
as
result,
have
developed
numerous
methodologies
to
afford
wide
variety
of
derivatives.
The
synthesis
recent
years
flourished,
employing
C─H
activation
strategies
using
various
transition
metal
catalysts:
rhodium
(Rh),
ruthenium
(Ru),
nickel
(Ni),
manganese
(Mn),
cobalt
(Co).
To
summarize
this
diverse
area
study,
review
comprehensively
assimilates
the
literature
where
isoquinolines
are
synthesized
alkynes
(both
internal
terminal)
coupling
partners.
Wherever
possible,
mechanistic
details
associated
with
reported
reactions
provided.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(10), P. 2091 - 2096
Published: March 5, 2024
Herein,
we
report
the
facile
synthesis
of
indole
C(4)-acrylophenone
using
a
C–H
bond
activation
strategy.
For
this
conversion,
an
unsymmetrical
alkyne
(phenylethynyl
ether)
in
presence
cobalt(III)-catalyst
works
efficiently.
In
process,
gets
oxidized
situ
generated
water,
which
is
key
step
for
method,
trifluoroethanol
water
source.
The
pivaloyl
directing
group
chelates
effectively
to
generate
cobaltacycle
intermediate,
was
detected
through
high-resolution
mass
spectrometry
(HRMS).
Also,
formation
bis(2,2,2-trifluoroethyl)
ether
has
been
confirmed
and
quantified
19F
NMR.
addition,
applicability
obtained
product
demonstrated
by
performing
Nazarov
cyclization
conjugate
addition
α,β-unsaturated
ketone
moiety.
The Chemical Record,
Journal Year:
2022,
Volume and Issue:
23(3)
Published: Dec. 13, 2022
Abstract
Transition
metal‐catalyzed
C−H
functionalization
of
diverse
arenes
with
alkyne
units
has
attracted
enormous
attention
for
decades
since
they
provide
straightforward
access
to
various
functionalization/annulations,
which
are
commonly
present
in
bioactive
compounds
and
natural
products.
Recently,
conjugated
alkynes
(1,3‐diynes)
have
been
utilized
as
key
coupling
partner
many
activation
reactions
due
their
versatile
characteristic
properties.
The
presence
two
C≡C
bonds
1,3‐diyne
brings
the
new
diversity
synthetic
transformations,
such
chemo‐,
regioselective
pathways,
mono‐bis
functionalizations,
cascade
annulations,
etc.
Herein,
we
summarized
latest
developments
realm
transition‐metal‐catalyzed
functionalizations
1,3‐diynes.
Moreover,
highlighted
conditions,
mechanisms
applications
corresponding
reaction
detail.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(12), P. 1977 - 1982
Published: June 2, 2023
Abstract
Herein,
we
report
the
reactivity
of
cobalt(III)‐catalyst
towards
hydroarylative
functionalization
1,6‐diyne,
which
has
never
been
explored
before.
The
N
‐aryl
lactam
is
prime
substrate
that
undergoes
sp
2
C−H
bond
activation.
C−Co(III)
formation
occurs
through
weakly
coordinating
group.
reaction
mechanism
reveals
in‐situ
a
six‐membered
cobaltacycle
further
with
1,6‐diyne.
Also,
radical
quenching
experiments
suggest
involvement
ionic
pathway
for
this
conversion.
In
addition,
hydrogen
scrambling
and
kinetic
isotope
support
proposed
mechanism.
A
wide
range
electronically
biased
substrates
reacting
partners
work
well
method
in
highly
atom‐economical
fashion.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(13), P. 8542 - 8552
Published: June 12, 2023
Functionalized
aryl(heteroaryl)
ketones
are
present
in
many
natural
products
as
key
structural
components
and
serve
basic
synthetic
building
blocks
for
various
organic
transformation
reactions.
Therefore,
the
development
of
an
effective
sustainable
route
making
these
classes
compounds
remains
challenging
yet
highly
desirable.
Herein,
we
report
a
simple
efficient
catalytic
system
dialkynylation
aromatic/heteroaromatic
via
double
C–H
bond
activation
presence
less
expensive
ruthenium(II)-salt
catalyst
using
weakly
native
carbonyl
group
desired
directing
group.
The
developed
protocol
is
compatible,
tolerant,
toward
functional
groups.
utility
has
been
demonstrated
through
scale-up
synthesis
transformation.
Control
experiments
support
involvement
base-assisted
internal
electrophilic
substitution
(BIES)
reaction
pathway.
