Russian Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
93(11), P. RCR5140 - RCR5140
Published: Oct. 30, 2024
The
urgency
of
improving
the
efficiency
known
methods
and
developing
new
ones
for
synthesis
unsaturated
silanes
is
caused
by
need
to
obtain
useful
compounds,
including
biologically
active
ones,
on
their
basis.
This
review
considers
preparation
silanes,
transformations
prospects
use
as
precursors
in
organic
organoelement
synthesis.
A
large
number
substituted
organosilicon
products
are
given,
those
capable
further
functionalization
formation
heterocycles,
silaheterocycles.<br>
bibliography
includes
205
references.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
16(15)
Published: Feb. 5, 2024
Abstract
The
selective
conversion
of
unsaturated
compounds
has
emerged
as
a
crucial
method
in
chemical
synthesis,
enabling
the
synthesis
functional
organic
molecules.
In
recent
decades,
transition
metal‐catalyzed
hydrosilylation
highly
successful
exemplar
industrialization
within
realm
chemistry
for
production
organosilanes,
which
have
pivotal
role
and
materials
science.
Precious
metal
complexes
are
typically
employed
catalysts
most
industrial
processes.
exploration
Earth‐abundant
alternatives
focal
point
considerable
research
attention
due
to
high
cost,
poor
selectivity,
many
side
reactions
reported
precious
catalysts.
Ligand
skeleton
construction,
mechanism
areas
where
cobalt
more
potential
than
iron
nickel.
This
review
discusses
advances
cobalt‐catalyzed
across
carbon‐carbon,
carbon‐oxygen,
carbon‐nitrogen
multiple
bonds
from
2019
2023.
ChemCatChem,
Journal Year:
2023,
Volume and Issue:
15(14)
Published: May 30, 2023
Abstract
Vinylsilanes
are
highly
appealing
and
convenient
chemical
derivatives,
as
evidenced
by
the
increasing
number
of
synthetic
transformations
utilizing
this
class
compounds.
Herein,
a
new
comprehensive
cobalt‐catalyzed
procedure
has
been
developed
enabling
selective
hydrosilylation
internal
aryl‐,
alkyl‐,
silylalkynes.
Cobalt
complexes
bearing
triazine‐based
PNP
pincer‐type
ligands
provide
exclusive
syn
‐addition
primary
well
secondary
silanes
to
C≡C
bonds.
As
result,
(
E
)‐silylalkenes
vicinal
disilylalkenes
were
effectively
obtained
with
excellent
stereoselectivity
regioselectivity.
Unlike
several
TM‐catalyzed
procedures,
no
external
additives
required
since
hydrosilanes
act
both
substrates
activators.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
16(15)
Published: March 18, 2024
Abstract
In
this
report,
we
have
synthesized
two
new
NCS
pincer
ligands
by
the
Schiff
base
reaction
of
3‐((phenylthio)methoxy)benzaldehyde
(
P
)
with
alkyl
amines
t
butylamine
L1
and
1‐adamantylamine
L2
)).
The
palladium
complexes
butylamine=
C1
1‐adamantylamine=
C2
these
were
their
PdCl
2
(CH
3
CN)
precursor.
newly
characterized
using
various
analytical
spectroscopic
techniques
such
as
1
H,
13
C{
H}
Nuclear
Magnetic
Resonance
(NMR),
Ultraviolet–visible
(UV‐Visible),
Fourier
Transform
Infrared
(FTIR)
Spectroscopy,
High‐Resolution
Mass
Spectrometry
(HRMS).
structure
ligand
its
coordination
mode
precursor
studied
help
single‐crystal
X‐ray
diffraction.
showed
distorted
square
planar
geometry
around
center.
used
catalysts
for
regioselective
cross‐dehydrogenative
alkenation
2‐arylthiophene
derivatives.
complex
,
where
sterically
bulky
adamantyl
is
part
side
arm
a
higher
yield
reaction.
Only
2.5
mol%
catalyst
loading
was
sufficient
to
achieve
74–95
%
yields
desired
products
excellent
functional
group
tolerance
under
mild
conditions.
poisoning
experiments
(PPh
Hg)
homogeneous
nature
catalytic
process.
plausible
mechanism
proposed
based
on
control
time‐dependent
HRMS
studies.
Heterogeneous
rhodium
catalysts
supported
on
phosphorus-rich
covalent
organic
polymers
provide
a
sustainable
solution
to
the
scarcity
of
Rh
resources
in
chemical
industry.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(13), P. 8133 - 8149
Published: June 15, 2023
In
recent
years,
catalysis
with
base
metal
manganese
has
received
a
significant
amount
of
interest.
Catalysis
complexes
having
N-heterocyclic
carbenes
(NHCs)
is
relatively
underdeveloped
in
comparison
to
the
extensively
investigated
catalysts
possessing
pincer
ligands
(particularly
phosphine-based
ligands).
Herein,
we
describe
synthesis
two
imidazolium
salts
decorated
picolyl
arms
(L1
and
L2)
as
NHC
precursors.
Facile
coordination
L1
L2
MnBr(CO)5
presence
resulted
formation
manganese(I)-NHC
(1
2)
an
air-stable
solid
good
isolated
yield.
Single-crystal
X-ray
analysis
revealed
structure
cationic
[Mn(CO)3(NHC)][PF6]
tridentate
N,C,N
binding
ligand
facile
fashion.
Along
few
known
manganese(I)
complexes,
these
Mn(I)-NHC
1
2
were
tested
for
hydrosilylation
terminal
alkynes.
Complex
was
proved
be
effective
catalyst
alkynes
selectivity
toward
less
thermodynamically
stable
β-(Z)-vinylsilanes.
This
method
provided
regioselectivity
(anti-Markovnikov
addition)
stereoselectivity
(β-(Z)-product).
Experimental
evidence
suggested
that
present
pathway
involved
organometallic
mechanism
manganese(I)-silyl
species
possible
reactive
intermediate.
Chemical Communications,
Journal Year:
2023,
Volume and Issue:
59(77), P. 11548 - 11551
Published: Jan. 1, 2023
A
new
catalytic
system,
based
on
an
octacarbonyl
dicobalt(0)
complex
and
bulky
ligand,
providing
a
route
to
α-vinylgermanes
is
described.
The
proposed
method
can
be
effectively
used
for
Markovnikov-selective
hydrogermylation
of
number
terminal
internal
alkynes.
It
has
been
proved
that
analogous
systems
containing
less
sterically
demanding
ligands
cannot
serve
as
selective
catalysts
in
this
transformation.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(16), P. 1860 - 1866
Published: April 18, 2024
Comprehensive
Summary
By
rational
modification
of
electronic
and
steric
properties
pincer
ligands,
a
Co/Fe
dual
catalyst
system
is
developed
for
one‐pot
sequential
Markovnikov
alkyne
hydrosilylation
stereoselective
alkene
isomerization.
The
protocol
provides
an
atom‐economical
efficient
approach
to
trisubstituted
(
E
)‐alkenyl
silanes
from
widely
accessible
terminal
alkynes
with
high
regio‐
stereoselectivities
under
mild
conditions.
utility
this
reaction
was
demonstrated
by
gram‐scale
synthesis
derivatization
bioactive
molecules.
radical
clock
trapping
experiments
indicated
that
pathway
might
be
operative
in
the
isomerization
step.
