International Journal of Molecular Sciences,
Год журнала:
2024,
Номер
25(14), С. 7894 - 7894
Опубликована: Июль 19, 2024
A
method
for
the
reduction
of
aldehydes
with
pinacolborane
catalyzed
by
pincer
cobalt
complexes
based
on
a
triazine
backbone
is
developed
in
this
paper.
The
presented
methodology
allows
transformation
several
bearing
wide
range
electron-withdrawing
and
electron-donating
groups
under
mild
conditions.
procedure
direct
one-step
hydrolysis
obtained
intermediates
to
corresponding
primary
alcohols.
plausible
reaction
mechanism
proposed.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(11), С. 2382 - 2431
Опубликована: Апрель 12, 2024
Abstract
This
contribution
offers
a
comprehensive
overview
of
methods
for
forging
sp
C−Si
bonds.
Over
time,
alkynylsilanes
(silylacetylenes),
once
considered
mere
byproducts
hydrosilylation
processes,
have
become
essential
building
blocks
in
organic
synthesis.
literature
review
traces
the
evolution
their
synthesis,
from
traditional
methodologies
relying
on
organolithium
and
organomagnesium
compounds
to
more
advanced
cross‐coupling
reactions
involving
hydro‐
carbosilanes.
Focused
primarily
past
25
years
(2000–2024),
it
also
extensively
references
significant
historical
breakthroughs.
By
analyzing
synthetic
methodologies,
not
only
survey
current
state
knowledge
but
identifies
areas
improvement.
Furthermore,
emphasize
importance
1‐alkynylsilanes
(1‐silyl‐1‐alkynes),
selected
applications
these
are
highlighted,
confirming
potential
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(12), С. 2775 - 2783
Опубликована: Апрель 24, 2024
Abstract
Achieving
precise
control
over
regioselectivity
and
stereoselectivity
in
the
hydroelementation
of
terminal
allenes
presents
a
formidable
challenge.
Despite
existence
various
catalytic
methods
for
their
functionalization,
this
entire
class
reactions
remains
significantly
underdeveloped
demands
extensive
research.
Here,
we
report
method
using
inexpensive
PN
5
P
pincer
cobalt
complexes
built
on
triazine
backbone.
Depending
substituent
at
ring,
enables
selective
synthesis
E‐alkenylsilane
or
Z‐allylborane
derivatives.
In
presented
approach,
silanes
pinacoloboranes
play
dualistic
role
simultaneous
activator
substrate
excluding
need
addition
external
bases.
Finally,
application
potential
obtained
compounds
was
demonstrated
by
performing
further
functionalizations
compounds.
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.
Inorganic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(12), С. 3656 - 3663
Опубликована: Янв. 1, 2023
Pincer
cobalt
complexes
based
on
a
triazine
backbone
have
been
used
as
efficient
catalysts
for
the
hydroboration
reaction
of
alkenes.
The
presented
protocol
shows
unique
selectivity
distinguishing
vinylsilyl
from
another
alkenyl
or
alkynyl
groups.
Abstract
A
cobalt‐catalyzed
addition
of
hydrosilanes
to
unsaturated
carbon‐oxygen
bonds
has
been
developed,
relying
on
complexes
featuring
easily
accessible
and
inexpensive
PNP‐type
pincer
ligands.
wide
range
heterocyclic,
aliphatic,
aromatic
ketones,
including
those
containing
both
electron‐donating
electron‐withdrawing
substituents,
were
transformed
into
silyl
ethers
or
secondary
alcohols
with
high
yields.
An
important
feature
this
protocol
is
that
silanes
can
act
as
the
substrates
activators,
eliminating
need
for
external
additives
such
strong
bases.
Organic Letters,
Год журнала:
2023,
Номер
25(35), С. 6528 - 6533
Опубликована: Авг. 30, 2023
The
functionalization
of
alkynylgermanes
using
hydrosilanes
was
accomplished
by
employing
cobalt
catalysis.
Depending
on
the
reactants
used,
reaction
can
proceed
via
dehydrogenative
coupling
or
hydrosilylation.
Importantly,
presented
method
is
characterized
mild
conditions,
allowing
rapid
access
to
a
wide
range
organogermanes.
Abstract
Cobalt
complexes
featuring
triazine‐based
PNP
ligands
have
proven
to
be
exceptionally
active
and
chemoselective
pre‐catalysts
in
facilitating
the
dehydrogenative
coupling
between
silanes
amines,
leading
synthesis
of
diverse
aminosilanes.
Notably,
even
challenging
substrates
exhibited
high
reactivity.
The
catalyst‘s
unique
feature
avoiding
with
tertiary
enhances
process
chemoselectivity.
It
facilitates
a
more
precise
silylamines
possessing
SiH
2
−N
SiH−N
motifs,
overcoming
challenges
associated
broader
reactivity
seen
previous
systems.
In
terms
its
remarkable
chemoselectivity,
it
is
also
noteworthy
that
catalytic
system
exhibits
both
versatility
efficacy
converting
untouched
double
triple
carbon‐carbon
bonds.
This
accomplishment
particularly
significant,
given
brought
about
by
activity
commonly
employed
catalysts
competitive
hydrosilylation
process.
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(15), С. 4125 - 4130
Опубликована: Янв. 1, 2024
A
highly
selective
and
scalable
dehydrative
approach
for
the
synthesis
of
unsymmetric
disiloxanes
polysiloxanes
is
reported
using
Earth-abundant
cobalt
catalyst
under
an
air
atmosphere.
