Transition
metal-catalyzed
C-H
activation
and
functionalization
with
various
coupling
partners
is
a
well-explored
area
of
research.
Among
the
used,
alkynes
occupy
prominent
position
on
account
their
varied
reactivity.
Due
to
low
steric
demand
high
degree
unsaturation
they
effectively
overlap
metal
d-orbitals
form
multiple
bond-forming
events
giving
rise
complex
skeletons
that
are
otherwise
challenging
synthesize.
This
makes
alkyne
one
most
successful
in
terms
number
useful
transformations.
Remarkably,
by
changing
reaction
conditions
transition-metals
from
5d
3d,
behaviors
also
change.
Despite
enormous
explorations
alkynes,
there
still
lot
more
possible
ways
which
can
be
made
react
M-C
bonds
generated
through
activation.
Especially
development
new
valent
first-row
catalysts,
plenty
scope
for
this
chemistry
evolve
as
explored
areas
research
coming
years.
Therefore,
review
topic
both
timely
synthetic
chemists
who
working
area.
In
review,
we
have
highlighted
diverse
reactivity
transition
metals
applications
along
some
our
thoughts
future
prospects.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(36)
Published: July 12, 2022
Herein,
we
leverage
the
Ni-catalyzed
enantioselective
reductive
dicarbofunctionalization
of
internal
alkenes
with
alkyl
iodides
to
enable
synthesis
chiral
pyrrolidinones
bearing
vicinal
stereogenic
centers.
The
application
newly
developed
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(14), P. 1673 - 1678
Published: Feb. 14, 2023
Comprehensive
Summary
Transition
metal‐catalyzed
difunctionalization
of
tethered
alkene
has
emerged
as
a
prevailing
tool
for
the
expedient
construction
synthetically
valuable
cyclic
compounds.
However,
most
efforts
have
been
devoted
to
reaction
styrene‐type
substrates
due
their
rigid
scaffold
and
high
reactivity.
With
respect
nonaromatic
olefin,
especially
mono‐substituted
alkene,
still
remains
largely
underdeveloped.
Herein,
we
disclose
nickel/Quinim
complex
TBADT‐cocatalyzed
asymmetric
carbamoyl‐acylation
unactivated
on
carbamoyl
chlorides
with
diverse
aldehydes.
The
exhibits
broad
substrate
scope
good
functional
group
tolerance,
well
efficiency
enantioselectivity.
Both
monosubstituted
1,1‐substituted
alkenes
can
work
either
aliphatic
or
aromatic
aldehydes
under
current
protocol,
providing
convenient
access
an
array
medicinally
useful
chiral
γ‐lactams
derivatives
bearing
convertible
acyl
functionality.
This
showcases
more
application
possibilities
Quinim
ligand
in
future
catalytic
transformations.
Organic Chemistry Frontiers,
Journal Year:
2021,
Volume and Issue:
8(14), P. 4024 - 4045
Published: Jan. 1, 2021
This
review
highlights
the
recent
advancements
of
carbamoyl
chlorides
in
transition
metal-catalyzed
reactions
to
access
various
amide-containing
molecules
and
heterocycles.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(21), P. 5650 - 5655
Published: Jan. 1, 2023
A
palladium-catalyzed
spirocyclization
reaction
is
reported,
which
proposed
to
arise
via
insertion
of
an
oxabicycle
into
a
palladacycle,
formed
from
carbocyclization
and
C-H
functionalization
sequence.
Mechanistic
studies
suggest
the
diastereoselective
post-catalytic
retro-Diels-Alder
step
furnishes
alkene,
wherein
oxibicycle
has
served
as
acetylene
surrogate.
Aryl
iodides
carbamoyl
chlorides
were
compatible
starting
materials
under
same
conditions,
enabling
convergent
complementary
synthesis
spirooxindoles,
well
other
azacycles.
These
spirooxindoles
allowed
further
transformations
that
previously
unaccessible.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(8), P. 1863 - 1876
Published: Feb. 21, 2024
Abstract
Ru(II)‐catalyzed
and
solvent‐switched
[3+2]‐spiroannulation
[4+n]
(n=1,
2,
3)
annulations
of
2‐aryl
quinazolinone
or
2‐aryl‐2,3‐dihydrophthalazine‐1,4‐diones
with
ynones
alkynyl
alcohol
1,3‐diynes
under
mild
reaction
conditions
have
been
analyzed.
These
reactions
take
place
in
the
presence
appropriate
solvent
features
a
redox‐neutral
pathway.
Ynone
serves
as
an
‘atypical
one‐carbon
unit’
[4+1]
annulation
generates
tetrasubstituted
carbon
center
bearing
diverse
heterocycles
through
[3+2]
strategies.
Post
transformations
synthesized
spiro‐products
augments
potential
developed
methodology.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(16), P. 6407 - 6411
Published: Aug. 4, 2021
Herein
we
report
a
nickel-catalyzed
asymmetric
reductive
dicarbamoylation
of
alkenes,
in
which
tethered
carbamoyl
chlorides
and
isocyanates
serve
as
distinct
electrophilic
carbamoylating
agents,
providing
new
access
to
chiral
oxindoles
bearing
an
amide-substituted
quaternary
stereogenic
center.
Chemical Communications,
Journal Year:
2022,
Volume and Issue:
58(74), P. 10262 - 10289
Published: Jan. 1, 2022
The
metal–carbon
bond
generated
through
C–H
activation
is
a
key
organometallic
intermediate,
which
could
be
further
functionalized
with
various
reacting
partners.
Among
the
coupling
partners
used
in
metal-catalysed
activation,
alkynes
occupy
prominent
position
on
account
of
their
varied
reactivity.
Asian Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
11(12)
Published: Nov. 22, 2022
Abstract
Spirocyclic
compounds
represent
an
imperative
class
of
naturally
occurring
substances
characterized
by
their
potential
biological
properties.
They
receive
much
attention
as
scaffolds
in
modern
drug
discovery
programs
and
widespread
applications
asymmetric
organic
synthesis
chiral
catalysts
ligands
because
structural
rigidity
excellent
stereochemical
recognition.
With
the
advent
C−H
activation/annulation,
enters
into
a
new
dimension
with
formation
novel
spiro
cycles.
The
present
review
highlights
advances
transition‐metal‐catalyzed
spirocyclic
triggered
bond
activation.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(50), P. 7751 - 7754
Published: Jan. 1, 2023
We
report
an
unprecedented
atom-economic
one-pot
Cp*Rh(III)-catalyzed
regioselective
[3+2]-spiroannulation
reaction
between
dibenz(ox)azepines
and
ynones,
allowing
the
synthesis
of
biologically
relevant
novel
spirocyclic
under
operationally
simple
mild
conditions.
The
proceeds
without
any
silver
additive
or
external
oxidant
implementing
a
redox-neutral
pathway.
A
broad
substrate
scope
with
diverse
functional
group
tolerance
permitted
wide
spectrum
indene-containing
in
good
to
excellent
yields.
Also,
we
showcased
detailed
mechanistic
studies
justify
formation
spirocycles.
In
addition,
synthetic
utility
this
process
was
also
demonstrated
by
modular
various
steroid
conjugates.
