Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(47)
Published: Aug. 22, 2024
Abstract
While
significant
progress
has
been
made
in
the
area
of
transition
metal‐catalyzed
ring‐opening
and
formal
cycloaddition
reactions
1,1‐disubstituted
silacyclobutanes
(SCBs),
synthesizing
these
SCBs—particularly
those
bearing
additional
functional
groups—continues
to
present
synthetic
challenges.
In
this
context,
we
a
novel
Ni‐catalyzed
reductive
coupling
reaction
that
combines
1‐chloro‐substituted
with
aryl
or
vinyl
halides
pseudohalides,
thereby
obviating
need
for
organometallic
reagents.
This
method
facilitates
generation
remarkable
tolerance
various
groups.
approach
serves
as
complementary
more
step‐economical
alternative
commonly
used
yet
moisture‐
air‐sensitive
nucleophilic
substitution
involving
Grignard
lithium
Our
initial
mechanistic
studies
indicate
is
initiated
by
oxidative
cleavage
Si−Cl
bond
1‐chlorosilacyclobutanes,
which
represents
distinct
mechanism
from
previously
documented
processes
carbon
electrophiles
chlorosilanes.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(16)
Published: Feb. 23, 2024
Herein,
we
successfully
inhibited
the
preferential
homodimerization
and
C-Si/Si-H
bond
cross-exchange
of
benzosilacyclobutenes
monohydro-silacyclobutanes
achieved
first
highly
selective
C-Si/C-Si
reaction
by
deliberately
tuning
Ni-catalytic
system,
which
constitutes
a
powerful
atom-economical
ring
expansion
method
for
preparing
medium-sized
cyclic
compounds
bearing
two
silicon
atoms
at
junction,
are
otherwise
inaccessible.
The
DFT
calculation
explicitly
elucidated
pivotal
role
Si-H
silacyclobutanes
high
strain
substrates
in
realizing
C-Si
bonds
cleavage
reformation
catalytic
cycle.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: March 12, 2025
Abstract
Increasing
attention
has
been
paid
to
silacyclobutanes
because
of
their
wide
application
in
ring
opening
and
extension
reactions.
However,
the
synthesis
functionalized
remains
an
unmet
challenge
limited
functional
group
tolerance
reactions
with
organometallic
reagents
chlorosilacyclobutanes.
Herein,
we
report
a
conceptually
different
solution
this
end
through
visible-light-induced
metal-free
hydrosilylation
unactivated
alkenes
hydrosilacyclobutanes.
A
range
diverse
groups
including
base-sensitive
acid,
alcohol
ketones
participated
reaction
smoothly.
In
particular,
first
dihydrosilacyclobutane
provides
facile
access
various
alkyl
monohydrosilacyclobutanes.
Unsymmetrical
dialkyl
have
also
synthesized
consecutive
one
pot.
The
mechanism
study
reveals
that
Lewis
basic
solvent
could
promote
generation
strained
silyl
radicals
by
direct
light
irradiation
without
redox-active
photocatalyst
thiol
catalyst
plays
important
role
accelerating
reaction.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(14), P. 10882 - 10892
Published: July 4, 2024
The
key
structure
of
β-aminosilanes
has
attracted
significant
interest
because
their
latent
biological
activities
in
the
field
medicinal
chemistry.
However,
structural
variety
been
significantly
constrained
by
absence
a
comprehensive
synthetic
approach.
Thus,
development
regiodivergent
catalytic
systems
for
construction
structurally
diverse
via
an
intermolecular
cycloaddition
strategy
would
represent
addition
to
limited
toolkit
available
synthesis.
We
herein
present
attractive
approach
synthesis
through
regioselective
N-allenamides
with
expansion
silacyclobutanes
catalyzed
Pd/PR3.
Just
selecting
suitable
protecting
group
N-allenamides,
regioselectivity
is
completely
switched
efficiently
provide
two
regioisomers
silacyclic
β-aminosilanes.
Two
regioselectivities
were
proceeded
during
migratory
insertion
and
reductive
elimination
process,
origin
which
could
be
well
rationalized
using
density
functional
theory
calculations.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(14), P. 3821 - 3826
Published: Jan. 1, 2024
Here
we
report
a
Ni-catalyzed
highly
regio-
and
stereoselective
ring
opening
reaction
of
SCBs
with
1,3-dienes
for
straightforward
facile
preparation
allylsilanes.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(16)
Published: Feb. 23, 2024
Abstract
Herein,
we
successfully
inhibited
the
preferential
homodimerization
and
C−Si/Si−H
bond
cross‐exchange
of
benzosilacyclobutenes
monohydro‐silacyclobutanes
achieved
first
highly
selective
C−Si/C−Si
reaction
by
deliberately
tuning
Ni‐catalytic
system,
which
constitutes
a
powerful
atom‐economical
ring
expansion
method
for
preparing
medium‐sized
cyclic
compounds
bearing
two
silicon
atoms
at
junction,
are
otherwise
inaccessible.
The
DFT
calculation
explicitly
elucidated
pivotal
role
Si−H
silacyclobutanes
high
strain
substrates
in
realizing
C−Si
bonds
cleavage
reformation
catalytic
cycle.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Jan. 18, 2025
The
diverse
utility
of
acyclic
vinylsilanes
has
driven
the
interest
in
synthesis
enantioenriched
bearing
a
Si-stereogenic
center.
However,
predominant
approaches
for
catalytic
asymmetric
generation
have
mainly
relied
on
transition
metal-catalyzed
reactions
alkynes
with
different
silicon
sources.
Here
we
successfully
realize
enantioselective
linear
silicon-stereogenic
good
yields
and
enantiomeric
ratios
from
simple
alkenes
under
rhodium
catalysis.
significance
this
transformation
lies
its
ability
to
achieve
regioconvergent
enantioconvergent
conversion,
efficiently
transforming
petroleum-derived
isomeric
mixtures
olefin
feedstocks
into
single
regio-
stereoisomer
product.
practicality
method
is
further
exemplified
by
downstream
transformations
these
leveraging
functionality
leaving
group
nature
aryl
substituent
as
well
development
chiral
π-conjugated
double
bond
systems.
