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.
Organic Chemistry Frontiers,
Journal Year:
2021,
Volume and Issue:
8(10), P. 2250 - 2255
Published: Jan. 1, 2021
We
report
efficient
domino
Heck-disilylation
and
Heck-monosilylation
of
alkene-tethered
carbamoyl
chlorides
with
hexamethyldisilane
under
mild
reaction
conditions.
Journal of Saudi Chemical Society,
Journal Year:
2023,
Volume and Issue:
27(4), P. 101658 - 101658
Published: May 27, 2023
An
asymmetric
catalysis
is
a
form
of
catalytic
reaction
wherein
chiral
catalyst
controls
the
production
molecule
to
favour
synthesis
one
stereoisomer
over
another.
It's
good
way
make
stereoisomeric
molecules
for
pharmacological
purposes.
Among
transition
metals,
copper
cost-effective,
plentiful,
and
less
poisonous
metal.
This
review
focused
on
transformations
in
last
fifteen
years.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 19, 2024
The
development
of
effective
synthetic
methods
to
construct
γ-lactams
bearing
a
chiral
α-quaternary
carbon
from
relatively
inert
C(O)–H
bonds
with
alkenes
has
been
an
elusive
challenge.
Herein,
we
used
naphthylamine-derived
phosphine
oxide
ligating
Ni
and
Al
bimetallic
catalyst
realize
carbonylative
cyclization
formyl
C–H
alkenes,
highly
regio-
enantioselectively
constructing
in
up
99%
yield
98%
ee.
These
proved
be
versatile
precursors
for
many
biologically
active
molecules.
Advanced Synthesis & Catalysis,
Journal Year:
2021,
Volume and Issue:
364(4), P. 794 - 801
Published: Dec. 16, 2021
Abstract
We
reported
a
palladium‐catalyzed
carbamoyl‐carbamoylation/carboxylation/thioesterification
of
alkene‐tethered
carbamoyl
chlorides
using
Mo(CO)
6
as
the
carbonyl
source.
The
reactions
were
typically
performed
with
good
functional
group
compatibility
and
tolerated
different
nucleophiles
(amines,
alcohols,
phenols,
thiols
water),
which
provided
new
access
to
amidated/esterificated/thioesterificated/carboxylated
oxindoles
or
lactams
bearing
an
all‐carbon
quaternary
stereocenter
under
CO
gas‐free
conditions.
Furthermore,
natural
product
mutation
divergent
late‐stage
derivatization
are
important
practical
features.
magnified
image
ChemistrySelect,
Journal Year:
2021,
Volume and Issue:
6(25), P. 6464 - 6467
Published: July 1, 2021
Abstract
Utilizing
a
palladium‐catalyzed
cascade
strategy,
we
have
developed
an
intermolecular
aryl‐carbamoylation
of
unactivated
alkenes
under
mild
conditions,
allowing
for
facile
access
to
diverse
aryl‐functionalized
oxindoles
from
alkene‐tethered
carbamoyl
chlorides
in
moderate
good
yields.
Organic & Biomolecular Chemistry,
Journal Year:
2023,
Volume and Issue:
21(35), P. 7129 - 7135
Published: Jan. 1, 2023
We
report
a
palladium-catalyzed
Heck-carbonylation
of
alkene-tethered
carbamoyl
chlorides
by
utilizing
aryl
formates
as
convenient
CO
surrogates.
One
C-O
and
two
C-C
bonds
are
constructed
to
give
diversiform
esterified
oxindoles/γ-lactams
bearing
an
all-carbon
quaternary
stereocenter
under
gas-free
conditions.
This
transformation
features
wide
substrate
scope
good
functional
group
tolerance
can
be
easily
applied
late-stage
functionalization.
Chemical Communications,
Journal Year:
2021,
Volume and Issue:
57(53), P. 6518 - 6521
Published: Jan. 1, 2021
A
domino
reaction
catalyzed
by
palladium
gives
access
to
tetrahydrofluorenone
scaffolds
with
full
regio-
and
stereoselectivity
in
a
single
step,
where
the
precursor
dienes
originate
from
naturally
occurring
benzoic
acid.
Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
134(36)
Published: July 12, 2022
Abstract
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
1‐Nap
Quinim
is
critical
for
formation
two
contiguous
stereocenters
in
high
yield,
enantioselectivity,
and
diastereoselectivity.
This
catalytic
system
also
improves
both
yield
enantioselectivity
α,α‐dialkylated
γ‐lactams.
Computational
studies
reveal
that
enantiodetermining
step
proceeds
a
carbamoyl‐Ni
I
intermediate
reduced
by
Mn
reductant
prior
intramolecular
migratory
insertion.
presence
t
‐butyl
group
ligand
leads
an
unfavorable
distortion
substrate
TS
minor
enantiomer.
Calculations
support
improvement
compared
p
‐tol
Quinim.
Asian Journal of Organic Chemistry,
Journal Year:
2021,
Volume and Issue:
11(2)
Published: Dec. 20, 2021
Abstract
A
palladium‐catalyzed
cascade
Heck
cyclization/3‐(2‐oxindolyl)methylation
on
intramolecular
amination
of
o
‐alkynylanilines
for
the
synthesis
indolylmethyl
oxindoles
is
developed.
This
protocol
exhibits
high
efficiency,
good
functional
group
tolerance
and
scalability
from
easily
accessible
starting
materials.
In
this
transformation,
chloroformylaniline
was
used
as
an
oxidative
reagent
‐alkynylaniline
a
3‐indolyl
precursor.
