European Journal of Inorganic Chemistry,
Год журнала:
2023,
Номер
unknown
Опубликована: Сен. 20, 2023
Abstract
The
incorporation
of
BN
units
in
organic
scaffolds
by
isoelectronic/isosteric
substitution
selected
CC
couples
has
emerged
as
an
efficient
tool
to
produce
new
materials
with
useful
properties
and
functions.
knowledge
about
BN‐doped
inorganic–organic
hybrid
polymers,
however,
is
still
rather
scarce.
This
especially
true
for
linear
or
cyclolinear
macromolecules
that
feature
longer
inorganic
chains.
Herein,
we
introduce
1,2,5‐azadiborolane
a
polymer
building
block
the
first
time.
An
attempt
apply
it
synthesis
poly(iminoborane)
resulted
after
only
two
B−N
coupling
events
formation
molecular
compound
comprising
chain
three
nitrogen
boron
atoms
–
confirmed
single‐crystal
X‐ray
diffractometry.
In
combination
p
‐phenylene
diamine‐based
co‐monomer,
accomplished
incorporate
into
considerable
weight
features
B
2
N
3
chain.
We
additionally
synthesized
small
model
characterized
crystallographically
well.
Comparison
UV‐vis
spectra
monomer,
oligomer,
revealed
systematic
red‐shifts
longest‐wavelength
absorption
band
increasing
number
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(28), С. 15071 - 15077
Опубликована: Июль 6, 2023
A
nickel-catalyzed
N-N
cross-coupling
for
the
synthesis
of
hydrazides
is
reported.
O-Benzoylated
hydroxamates
were
efficiently
coupled
with
a
broad
range
aryl
and
aliphatic
amines
via
nickel
catalysis
to
form
in
an
up
81%
yield.
Experimental
evidence
implicates
intermediacy
electrophilic
Ni-stabilized
acyl
nitrenoids
formation
Ni(I)
catalyst
silane-mediated
reduction.
This
report
constitutes
first
example
intermolecular
coupling
compatible
secondary
amines.
Organic Letters,
Год журнала:
2023,
Номер
25(47), С. 8419 - 8423
Опубликована: Ноя. 20, 2023
Recent
advances
in
single-atom
insertion
reactions
have
opened
up
new
synthetic
approaches
for
molecular
diversification.
Developing
innovative
strategies
to
directly
transform
biologically
relevant
molecules,
without
any
prefunctionalization,
is
key
further
expanding
the
scope
and
utility
of
such
transformations.
Herein,
direct
access
quinazolines
pyrimidines
from
corresponding
unprotected
1H-indoles
1H-pyrroles
reported,
relying
on
implementation
lithium
bis(trimethylsilyl)amide
(LiHMDS)
as
a
novel
nitrogen
atom
source
combination
with
commercially
available
hypervalent
iodine
reagents.
Further
application
this
strategy
late-stage
settings
demonstrates
its
potential
lead
structure
diversification
campaigns.
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
Chemical Communications,
Год журнала:
2023,
Номер
59(25), С. 3665 - 3684
Опубликована: Янв. 1, 2023
This
article
covers
historical
and
recent
efforts
to
catalyse
the
dehydrocoupling
of
amines
silanes,
a
direct
method
for
Si-N
bond
formation
that
offers
hydrogen
as
byproduct.
In
some
applications,
this
transformation
can
be
used
sustainable
replacement
traditional
aminosilane
synthesis,
which
demands
corrosive
chlorosilanes
while
generating
one
equivalent
ammonium
salt
waste
each
is
formed.
These
advantages
have
driven
development
catalysts
span
periodic
table,
affording
mechanistic
insight
has
led
advances
in
efficiency
selectivity.
Given
divergence
precursors
being
used,
characterization
methods
relied
on,
applications
targeted,
highlights
monomeric
aminosilanes
separately
from
oligomeric
polymeric
aminosilanes.
A
study
allowed
manganese
catalysed
synthesis
perhydropolysilazane
commercial
chemical
vapor
deposition
featured,
key
opportunities
advancing
field
catalysis
are
discussed.
Chemical Communications,
Год журнала:
2023,
Номер
59(10), С. 1258 - 1273
Опубликована: Янв. 1, 2023
An
examination
of
several
catalytic
reactions
among
the
group
15
elements
is
presented.
The
connections
between
chemistry
pnictogens
can
sometimes
be
challenging,
but
aspects
metal-pnictogen
reactivity
are
key.
connecting
comes
from
metal-catalyzed
transformations
such
as
dehydrocoupling
and
hydrofunctionalization.
Pivotal
mechanistic
insights
E-N
heterodehydrocoupling
have
informed
development
highly
active
catalysts
for
these
reactions.
Metal-amido
nucleophilicity
often
at
core
this
reactivity,
which
diverges
phosphine
arsine
dehydrocoupling.
Nucleophilicity
connects
to
earliest
understanding
hydrophosphination
catalysis,
more
recent
leveraging
enhanced
insertion
activity
through
photolysis.
This
photocatalysis
extends
hydroarsination,
may
also
metal-arsenido
than
anticipated.
However,
arsinidene
foreshadowed
related
phosphinidene
by
years.
shows
potential
greater
influence
individual
discoveries
leverage
new
advances
elements,
it
suggests
that
heavier
on
what
possible
with
lighter
elements.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(20), С. 4237 - 4244
Опубликована: Янв. 1, 2023
An
N-heterocyclic
carbene-zinc
alkyl
complex
[ImDippZn(CH2CH3)2]
(Im
=
imidazol-2-ylidene
and
Dipp
2,6-diisopropylphenyl)
acts
as
a
catalyst
in
the
cross-dehydrogenative
coupling
(CDC)
of
wide
range
primary
secondary
amines
hydrosilanes
to
yield
substantial
quantity
corresponding
aminosilanes
with
good
chemoselectivity
at
room
temperature.
A
broad
substrate
scope
was
observed
during
zinc-catalyzed
CDC
reaction.
Two
zinc
complexes,
[{ImMesZn(μ-NHPh)(NHPh)}2]
(Mes
mesityl)
(3)
[{ImDippZn(CH2CH3)(μ-H)}2]
(4),
were
isolated
structurally
characterized
intermediates
through
controlled
reactions
ascertain
mechanism.
Chemical Communications,
Год журнала:
2022,
Номер
58(81), С. 11386 - 11389
Опубликована: Янв. 1, 2022
The
catalytic
synthesis
of
silylamines
mediated
by
s-
and
p-block
catalysts
is
largely
underdeveloped.
Herein,
commercially
available
potassium
bis(trimethylsilyl)amide
serves
as
an
efficient
alternative
to
transition
metal
complexes.
N-H/Si-C
dealkynative
coupling
was
achieved
means
user-friendly
main-group
catalysis
with
ample
substrate
scope
high
chemoselectivity.
Inorganic Chemistry,
Год журнала:
2023,
Номер
62(31), С. 12213 - 12222
Опубликована: Июль 23, 2023
The
N,N'-chelated
conjugated
bis-guanidinate
(CBG)
supported
zinc
hydride
(Zn-1)
pre-catalyzed
highly
challenging
chemoselective
mono-hydrosilylation
of
a
wide
range
nitriles
to
exclusive
N-silylimines
and/or
N,N'-silyldiimines
is
reported.
Furthermore,
the
effectiveness
pre-catalyst
Zn-1
compared
with
another
analogue,
i.e.,
DiethylNacNac
(Zn-2),
know
ligand
effect.
We
observed
that
shows
high
efficiency
and
better
selectivity
than
Zn-2
for
reducing
N-silylimines.
Mechanistic
studies
indicate
insertion
C≡N
bond
nitrile
into
Zn-H
form
vinylidenamido
complexes
(Zn-1'
Zn-2').
active
catalysts
Zn-1'
Zn-2'
are
confirmed
by
NMR,
mass
spectrometry,
single-crystal
X-ray
diffraction
analyses.
A
most
plausible
catalytic
cycle
has
been
explored
depending
on
stoichiometric
experiments,
isolation,
in
situ
studies.
Moreover,
synthetic
utility
this
protocol
was
demonstrated.
