ABSTRACT:
We
report
a
highly
enantioselective
intermolecular
silylation
of
the
propargylic
C(sp3)−H
bonds
alkynes
for
formation
silanes.
The
optimized
protocol
afforded
enantioenriched
α-silylated
in
good
to
high
yield
with
excellent
levels
stereocontrol
under
mild
conditions.
A
variety
silyl
triflates,
either
commercial
or
situ-generated,
were
used
as
reagents,
and
broad
range
simple
functionalized
alkynes,
including
aryl
alkyl
acetylenes,
dialkyl
1,3-enynes,
successfully
employed
substrates.
In
case
acetylene
substrates,
took
place
regi-oselective
manner.
Preliminary
mechanistic
experiments
suggest
catalytic
cycle
which
electrophilic
addition
triflate
reagent
Ir
center
subsequent
deprotonation
dicationic
Ir–alkyne
complex
are
key
steps.
Synlett,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 19, 2025
Abstract
Cyclometalated
complexes,
including
those
with
pincer
ligands
and
other
chelating
frameworks,
such
as
porphyrin
rings
polyenes,
have
garnered
significant
attention
due
to
their
diverse
applications
in
ion
analyte
detection
across
synthetic
chemistry,
environmental
monitoring,
medicine,
electronics.
These
complexes
exhibit
fascinating
chromic
behaviors,
mechanochromism,
chemochromism,
vapochromism,
which
are
particularly
useful
sensing
applications.
Of
particular
interest
photophysical
properties,
especially
involving
lanthanides,
offer
unique
luminescent
optical
characteristics.
Metals
nickel
(Ni),
palladium
(Pd),
ruthenium
(Ru),
gold
(Au),
rhodium
(Rh)
been
extensively
studied
order
understand
photochemical
activity
explore
potential
light-emitting
devices,
photo-induced
electron
transfer,
technologies.
Their
vapochromic
mechanochromic
properties
make
them
highly
attractive
for
sensing,
while
photoluminescent
capabilities
enhance
utility
optoelectronic
devices
practical
This
review
provides
a
comprehensive
overview
of
applications,
gas,
cation,
anion
sensing.
The
discussion
also
highlights
the
need
incorporate
specific
examples
that
demonstrate
suitability
these
targeted
tasks,
further
emphasizing
promise
advancing
sensor
device
1
Introduction
2
Strategies
3
Applications
4
Other
Miscellaneous
Examples
5
Drawbacks
Limitations
6
Conclusion
Perspectives
7
List
Abbreviations
Definitions
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(30)
Published: May 25, 2023
Abstract
Hydrofunctionalization
of
alkynes
is
one
the
most
efficient
ways
to
access
axially
chiral
styrenes
with
open‐chained
olefins.
While
great
advances
have
been
achieved
for
1‐alkynylnaphthalen‐2‐ols
and
analogues,
atroposelective
hydrofunctionalization
unactivated
internal
lags.
Herein
we
reported
a
platinum‐catalyzed
hydrosilylation
first
time.
With
monodentate
TADDOL‐derived
phosphonite
L1
used
as
ligand,
various
were
in
excellent
enantioselectivities
high
E
‐selectivities.
Control
experiments
showed
that
N
H‐arylamide
groups
significant
effects
on
both
yields
could
act
directing
groups.
The
potential
utilities
products
shown
by
transformations
amide
motifs
products.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(12), P. 6861 - 6870
Published: March 14, 2023
Despite
the
notable
advances
achieved
in
Murai-type
hydroarylations,
highly
enantioselective
catalytic
addition
of
native
(hetero)arenes
to
internal
alkenes
remains
a
prominent
challenge.
Herein,
we
report
directing
group
repositioning
strategy,
which
enables
iridium-catalyzed
heteroarenes
including
furan,
benzofuran,
and
thiophene
enamides.
The
C-H
bond
at
C2
position
heteroarene
is
site-selectively
cleaved
added
regioselectively
β-position
an
enamide,
affording
valuable
β-heteroaryl
amide
with
high
enantioselectivity.
Mechanistic
studies
indicate
that
rate
enantioselectivity
are
determined
by
separate
elementary
steps.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(6)
Published: Dec. 14, 2023
Abstract
Metal‐catalyzed
asymmetric
C−H
bond
annulation
strategy
offers
a
versatile
platform,
allowing
the
construction
of
complex
P‐chiral
molecules
through
atom‐
and
step‐economical
fashion.
However,
regioselective
insertion
π‐coupling
partner
between
M−C
with
high
enantio‐induction
remain
elusive.
Using
commercially
available
Co(II)
salt
chiral‐Salox
ligands,
we
demonstrate
an
unusual
protocol
for
regio‐reversal,
enantioselective
phosphinamide
bromoalkyne
desymmetrization.
The
reaction
proceeds
ligand‐assisted
enantiodetermining
cyclocobaltation
followed
by
Co−C,
subsequent
reductive
elimination,
halogen
exchange
carboxylate
resulted
in
P‐stereogenic
compounds
excellent
ee
(up
to
>99
%).
isolation
cobaltacycle
involved
catalytic
cycle
outcome
control
experiments
provide
support
plausible
mechanism.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(5), P. 2872 - 2882
Published: Feb. 9, 2024
Readily
available
N-carbamoyl
indolines
can
be
converted
into
highly
valuable
2-alkenyl
and
2-alkyl
indoles
in
a
one-pot
reaction,
through
an
autotandem
catalytic
cascade
promoted
by
iridium
complex.
The
process
entails
dehydrogenation
reaction
initiated
iridium-promoted
C(sp3)–H
activation,
the
addition
of
resulting
indole
to
alkyne
-or
alkene-partner,
spontaneous
loss
carbamoyl
directing
group.
Interestingly,
C2-alkenyl
participate
variety
metal-catalyzed
annulations
C–H
including
formal
[4
+
1]
2]
cycloadditions,
as
well
cross-dehydrogenative
cyclizations,
thus
enabling
divergent
access
collection
functionally
rich
nitrogen-containing
heterocycles.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(23), P. 8888 - 8895
Published: Jan. 1, 2024
A
highly
efficient
method
achieves
precise
construction
of
alkyl
chiral
centers
at
remote
C3-positions
in
five-membered
S/O-heterocycles
via
cobalt-catalyzed
asymmetric
hydroalkylation
heterocyclic
alkenes.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(12), P. 9294 - 9301
Published: June 4, 2024
A
cobalt-catalyzed
hydroalkynylation
of
alkenes
with
alkynyl
trifluoroborates
is
described,
proceeding
through
a
cobalt
hydride-mediated
radical-polar
crossover
metal
hydrogen-atom-transfer
process.
This
method
affords
structurally
diverse
alkynyl-containing
compounds
in
high
yields
under
mild
conditions
and
features
wide
substrate
scope,
good
functional
group
tolerance,
suitability
for
late-stage
functionalization
relatively
complex
natural
products
bioactive
molecules.
Expanding
the
scope
to
alkenyltrifluoroborate
salts
further
increases
utility
developed
methodology.
approach
paves
an
alternative
route
radical-involved
alkynylation
alkenylation
reactions
nucleophilic
alkynyl/alkenyl
reagents.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
146(1), P. 723 - 732
Published: Dec. 20, 2023
Despite
the
current
progress
achieved
in
asymmetric
hydroacylations,
highly
enantioselective
catalytic
addition
of
unfunctionalized
aldehydes
to
internal
alkenes
remains
an
unsolved
challenge.
Here,
using
a
coordination-assisted
strategy,
we
developed
rhodium-catalyzed
regio-
and
such
as
enamides
β,γ-unsaturated
amides.
Valuable
α-amino
ketones
1,4-dicarbonyl
compounds
were
directly
obtained
with
high
enantioselectivity
from
readily
available
materials.
