Organic & Biomolecular Chemistry,
Год журнала:
2025,
Номер
23(19), С. 4636 - 4640
Опубликована: Янв. 1, 2025
The
solvent-free
mechanochemical
method
enables
efficient
synthesis
of
diverse
organothianthrenium
salts
via
ball-milling
technique,
eliminating
the
need
for
hazardous
reactants,
inert
atmosphere,
and
complex
reaction
setups.
Chemical Science,
Год журнала:
2023,
Номер
14(44), С. 12477 - 12483
Опубликована: Янв. 1, 2023
Iconic
Lappert's
heavier
tetrylenes
E{N(SiMe3)2}2
(E
=
Ge
(1),
Sn
(2),
Pb
(3))
have
been
efficiently
prepared
from
GeCl2·(1,4-dioxane),
SnCl2
or
PbCl2
and
Li{N(SiMe3)2}
via
a
completely
solvent-free
one-pot
mechanochemical
route
followed
by
sublimation.
This
fast,
high-yielding
scalable
approach
(2
has
in
100
mmol
scale),
which
involves
small
environmental
footprint,
represents
remarkable
improvement
over
any
synthetic
reported
the
last
five
decades,
being
so
far
rare
example
of
use
mechanochemistry
realm
main
group
chemistry.
solventless
successfully
extended
to
preparation
other
tetrylenes,
such
as
ECl{N(SiMe3)2}
(4),
(5)).
Chemistry - A European Journal,
Год журнала:
2023,
Номер
29(40)
Опубликована: Май 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
.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(26)
Опубликована: Янв. 31, 2024
Although
the
3
d
transition-metal
catalyzed
C-H
functionalization
have
been
extensively
employed
to
promote
formation
of
valuable
carbon-carbon
bonds,
persistent
problems,
including
use
sensitive
Grignard
reagents
and
rigorous
operations
(solvent-drying,
inert
gas
protection,
metal
pre-activation
RMgX
addition
rate
control),
still
leave
great
room
for
further
development
sustainable
methodologies.
Herein,
we
report
a
mechanochemical
technology
toward
in-situ
preparation
highly
organomagnesium
reagents,
thus
building
two
general
catalytic
platforms
that
enables
regioselective
arylation
alkylation
indoles
with
wide
variety
halides
(including
those
containing
post
transformable
functionalities
heteroaromatic
rings).
This
strategy
also
brings
unique
reactivity
high
step-economy
in
producing
functionalized
N-free
indole
products.
Organic & Biomolecular Chemistry,
Год журнала:
2025,
Номер
23(19), С. 4636 - 4640
Опубликована: Янв. 1, 2025
The
solvent-free
mechanochemical
method
enables
efficient
synthesis
of
diverse
organothianthrenium
salts
via
ball-milling
technique,
eliminating
the
need
for
hazardous
reactants,
inert
atmosphere,
and
complex
reaction
setups.