Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
147(6), P. 5426 - 5431
Published: Jan. 31, 2025
A
silylium-ion-promoted
α-C-H
allenylation
of
silyl
ethers
tethered
to
an
internal
alkyne
is
described.
The
actual
intermolecular
event
occurs
after
the
trans-selective
hydrosilylation
alkyne,
where
in
situ-generated
β-silicon-stabilized
vinyl
cation
engages
intramolecular
[1,5]-hydride
shift.
This
process
transforms
ether
into
a
silylcarboxonium
ion,
which
reacts
with
propargylsilanes
as
nucleophiles,
formed
by
rapid
silylium-ion-catalyzed
isomerization
allenylsilanes.
As
part
step,
propagating
silylium-ion
electrophile
regenerated,
thereby
closing
catalytic
cycle.
An
allylsilane
also
applicable
this
transformation,
producing
corresponding
allylation
product
high
yield.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
121(20), P. 12784 - 12965
Published: Aug. 27, 2021
This
review
serves
to
document
advances
in
the
synthesis,
versatile
bonding,
and
reactivity
of
molecular
main
group
metal
hydrides
within
Groups
1,
2,
12–16.
Particular
attention
will
be
given
emerging
use
said
rapidly
expanding
field
Main
Group
element-mediated
catalysis.
While
this
is
comprehensive
nature,
focus
research
appearing
open
literature
since
2001.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
121(10), P. 5889 - 5985
Published: April 16, 2021
The
history
of
silyl
cations
has
all
the
makings
a
drama
but
with
happy
ending.
Being
considered
reactive
intermediates
impossible
to
isolate
in
condensed
phase
for
decades,
their
actual
characterization
solution
and
later
solid
state
did
only
fuel
discussion
about
existence
initially
created
lot
controversy.
This
perception
completely
changed
today,
donor-stabilized
congeners
are
now
widely
accepted
compounds
promising
use
synthetic
chemistry.
review
provides
comprehensive
summary
fundamental
facts
principles
chemistry
cations,
including
reliable
ways
preparation
as
well
physical
chemical
properties.
striking
features
enormous
electrophilicity
such
reactivity
super
Lewis
acids
fluorophilicity.
Known
applications
rely
on
reactants,
stoichiometric
reagents,
promoters
where
reaction
success
is
based
steady
regeneration
over
course
reaction.
Silyl
can
even
be
discrete
catalysts,
thereby
opening
next
chapter
way
into
toolbox
methodology.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(31)
Published: May 11, 2024
The
use
of
noncovalent
interactions
based
on
electrophilic
halogen,
chalcogen,
pnictogen,
or
tetrel
centers
in
organocatalysis
has
gained
noticeable
attention.
Herein,
we
provide
an
overview
the
most
important
developments
last
years
with
a
clear
focus
experimental
studies
and
catalysts
which
act
via
such
non-transient
interactions.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(4), P. 1367 - 1372
Published: Feb. 1, 2021
An
asymmetric
synthesis
of
silicon-stereogenic
monohydrosilanes
by
rhodium-catalyzed
dehydrogenative
C–H
silylation
is
developed.
The
process
suitable
for
the
various
asymmetrically
trisubstituted
1H-benzosiloles
and
1H-benzosilolometallocenes
in
good
yields
with
excellent
chemo-,
regio-,
stereocontrol.
These
selected
1H-benzosilole
compounds
exhibit
bright
blue
fluorescence
CPL
(circular
polarized
luminescence)
signals,
which
could
be
attractive
to
practitioners
materials
science.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(9), P. 2275 - 2288
Published: Jan. 1, 2023
An
easy-to-perform
approach
to
assess
and
quantify
steric
properties
of
Lewis
acids
is
reported.
The
novel
LAB-Rep
model
(Lewis
acid/base
repulsion
model)
introduced,
which
judges
in
pairs.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(22)
Published: March 13, 2024
The
quantification
of
Lewis
acidity
is
fundamental
and
applied
importance
in
chemistry.
However,
if
neutral
charged
acids
are
compared,
a
coherent
ranking
has
been
elusive,
severe
uncertainties
were
accepted.
With
this
study,
we
present
systematic
computational
analysis
base
affinities
784
mono-,
di-
tricationic
their
comparison
with
149
representative
acids.
Evaluating
vacuum
fluoride
ion
(FIA)
reveals
charge-caused
clustering
that
prohibits
any
meaningful
ranking.
Instead,
solvation-corrected
FIA
Dalton Transactions,
Journal Year:
2020,
Volume and Issue:
49(21), P. 7060 - 7068
Published: Jan. 1, 2020
A
comprehensive
reactivity
study
of
an
acyclic
iminosiloxysilylene
provides
further
insights
into
this
relatively
unexplored
compound
class
and
revealed
analogies
to
both
classical
transition
metal
complexes
the
lighter
silicon
congener
carbon.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(38), P. 16493 - 16505
Published: Aug. 24, 2020
An
efficient
catalytic
method
to
convert
an
α-C–H
bond
of
N-alkylamines
into
α-C–alkynyl
was
developed.
In
the
past,
such
transformations
were
carried
out
under
oxidative
conditions,
and
enantioselective
variants
confined
tetrahydroisoquinoline
derivatives.
Here,
we
disclose
a
for
union
trimethylsilyl
alkynes,
without
presence
external
oxidant
promoted
through
cooperative
actions
two
Lewis
acids,
B(C6F5)3
Cu-based
complex.
A
variety
propargylamines
can
be
synthesized
in
high
diastereo-
enantioselectivity.
The
utility
approach
is
demonstrated
by
late-stage
site-selective
modification
bioactive
amines.
Kinetic
investigations
that
shed
light
on
various
mechanistic
nuances
process
are
presented.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(18), P. 6817 - 6822
Published: April 28, 2021
Practical,
efficient,
and
general
methods
for
the
diversification
of
N-heterocycles
have
been
a
recurrent
goal
in
chemical
synthesis
due
to
ubiquitous
influence
these
motifs
within
bioactive
frameworks.
Here,
we
describe
direct,
catalytic,
selective
functionalization
azines
via
silylium
activation.
Our
catalyst
design
enables
mild
conditions
remarkable
functional
group
tolerance
one-pot
setup.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(38), P. 15490 - 15507
Published: Sept. 14, 2021
Superacidic
media
became
famous
in
connection
with
carbocations.
Yet
not
all
reactive
intermediates
can
be
generated,
characterized,
and
eventually
isolated
from
these
Brønsted
acid/Lewis
acid
cocktails.
The
counteranion,
that
is
the
conjugate
base,
systems
often
too
nucleophilic
and/or
engages
redox
chemistry
newly
formed
cation.
acidity,
especially
superacidity,
fact
even
crucial
unless
protonation
of
extremely
weak
bases
needs
to
achieved.
Instead,
it
chemical
robustness
aforementioned
counteranion
determines
success
protolysis.
advent
molecular
superacids
derived
weakly
coordinating,
redox-inactive
counteranions
do
withstand
enormous
reactivity
superelectrophiles
such
as
silicon
cations
completely
changed
whole
field.
This
Perspective
summarizes
general
aspects
medium
acidity
shows
how
applications
have
advanced
stoichiometric
reactions
catalytic
processes
involving
protons
situ
generated
superelectrophiles.
