Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(7), P. 1509 - 1516
Published: Feb. 19, 2024
Abstract
The
reaction
of
chlorosilanes
with
organometallic
reagents
is
an
old
and
well‐developed
approach
to
organosilicon
compounds,
however,
its
application
was
limited
due
the
sensitivity
air,
water.
Here
we
display
a
mechanochemical
access
arylsilanes
via
Barbier‐type
aryl
halide
magnesium.
By
treatment
two
halides
Mg
powder
under
electromagnetic
milling,
series
are
obtained
within
15
minutes.
Taking
advantages
this
protocol
features
transition‐metal
free,
good
functional
group
tolerance,
air
stable
mild
conditions.
Molecules,
Journal Year:
2025,
Volume and Issue:
30(5), P. 1060 - 1060
Published: Feb. 26, 2025
An
efficient
and
air-tolerant
Ni-catalyzed
denitrogenative
cross-electrophile
coupling
of
benzotriazinones
with
benzyl
chlorides
has
been
developed
via
liquid-assisted
grinding
by
using
Mn
powders
as
reductant
DMF
assisting
liquid
in
the
presence
anhydrous
calcium
chloride.
Scope
limitations
protocol
to
access
diarylmethanes
have
demonstrated
more
than
20
examples,
showing
acceptable
tolerance
functional
group
steric
hindrance.
Although
electron-withdrawing
substituents
on
benzotriazinone
or
counterparts
decrease
yields
significantly,
a
series
N-alkyl-2-benzylbenzamides,
bearing
an
ortho-carbamoyl
aryl
group,
could
be
obtained
modest
good
yields.
Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(40)
Published: May 16, 2023
The
alkaline-earth
metals
Mg
and
Ca
are
too
inert
for
the
direct
metalation
of
primary
secondary
amines.
Consequently,
activation
prior
to
use
is
required.
Alternatively,
Grignard
reagents
RMgX
(R=alkyl,
aryl,
X=halide)
can
be
applied
in
However,
such
a
straightforward
procedure
synthesis
alkylcalcium
disadvantageous
due
diverse
side
reactions,
including
Wurtz-type
C-C
coupling
ether
degradation
reactions.
Therefore,
suspensions
magnesium
or
calcium
with
amine
treated
smooth
reaction
ethyl
bromide
an
ethereal
solvent
at
room
temperature.
Intermediately
formed
RAeX
(Ae=alkaline-earth
metal,
i.
e.,
Mg,
Ca)
either
metalates
amines
yielding
corresponding
amides
situ
method
(iGMM)
adds
across
C=N
bonds
imines
addition
(iGAM).
R'2
N-AeX
(Ae=Mg:
Hauser
bases)
undergo
Schlenk-type
ligand
exchange
reactions
homoleptic
Ae(NR'2
)2
potentially
sparingly
soluble
AeX2
.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(39)
Published: June 30, 2023
Organomagnesium
halides
(Grignard
reagents)
are
essential
carbanionic
building
blocks
widely
used
in
carbon-carbon
and
carbon-heteroatom
bond-forming
reactions
with
various
electrophiles.
In
the
Barbier
variant
of
Grignard
synthesis,
generation
air-
moisture-sensitive
reagents
occurs
concurrently
their
reaction
an
electrophile.
Although
operationally
simpler,
classic
approach
suffers
from
low
yields
due
to
multiple
side
reactions,
thereby
limiting
scope
its
application.
Here,
we
report
a
mechanochemical
adaptation
Mg-mediated
reaction,
which
overcomes
these
limitations
facilitates
coupling
versatile
organic
(e.g.,
allylic,
vinylic,
aromatic,
aliphatic)
diverse
range
electrophilic
substrates
aromatic
aldehydes,
ketones,
esters,
amides,
O-benzoyl
hydroxylamine,
chlorosilane,
borate
ester)
assemble
C-C,
C-N,
C-Si,
C-B
bonds.
The
has
advantage
being
essentially
solvent-free,
simple,
immune
air,
surprisingly
tolerant
water
some
weak
Brønsted
acids.
Notably,
solid
ammonium
chloride
was
found
improve
ketones.
Mechanistic
studies
have
clarified
role
mechanochemistry
process,
indicating
transient
organometallics
facilitated
by
improved
mass
transfer
activation
surface
magnesium
metal.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(7), P. 1509 - 1516
Published: Feb. 19, 2024
Abstract
The
reaction
of
chlorosilanes
with
organometallic
reagents
is
an
old
and
well‐developed
approach
to
organosilicon
compounds,
however,
its
application
was
limited
due
the
sensitivity
air,
water.
Here
we
display
a
mechanochemical
access
arylsilanes
via
Barbier‐type
aryl
halide
magnesium.
By
treatment
two
halides
Mg
powder
under
electromagnetic
milling,
series
are
obtained
within
15
minutes.
Taking
advantages
this
protocol
features
transition‐metal
free,
good
functional
group
tolerance,
air
stable
mild
conditions.
