Research Square (Research Square),
Journal Year:
2023,
Volume and Issue:
unknown
Published: Feb. 1, 2023
Abstract
We
report
a
copper-catalyzed
ligand-controlled
selective
1,2-
and
1,4-hydrosilylation
of
1,3-enynes,
which
furnishes
enantiomerically
enriched
propargyl-
1,2-allenylsilane
products
in
high
yields
with
excellent
enantioselectivities
(up
to
99%
ee).
This
reaction
proceeds
under
mild
conditions,
shows
broad
substrate
scope
for
both
1,3-enynes
trihydrosilanes,
displays
regioselectivities.
Mechanistic
studies
based
on
deuterium-labeling
reactions
density
functional
theory
(DFT)
calculations
suggest
that
allenylcopper
is
the
dominant
reactive
intermediate
it
undergoes
metathesis
silanes
via
four-membered
or
six-membered
transition
state,
depending
nature
ligand.
The
weak
interactions
between
ligands
reacting
partners
are
found
be
key
controlling
factor
observed
regioselectivity
switch.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(11), P. 2287 - 2291
Published: March 8, 2024
A
simple
and
efficient
Rh2(OAc)4/DPPM
(bis(diphenylphosphanyl)methane)
catalyzed
regioselective
1,2-anti-Markovnikov
hydrosilylation
of
conjugated
dienes
with
various
tertiary
silanes
gave
homoallylic
in
acetonitrile,
which
tolerate
broad
functional
groups.
Control
experiments
proved
that
no
π-allyl
transition
metal
intermediates
were
involved
this
hydrosilylation.
Dirhodium
hydride
species
was
observed
hydrosilylation,
suggesting
a
direct
insertion
the
terminal
double
bond
into
Rh–H
is
reaction.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(32), P. 6054 - 6059
Published: Aug. 10, 2022
A
novel
strategy
of
copper-catalyzed
regio-
and
enantioselective
hydrosilylation
4-substituted
vinylidenecyclohexanes
with
silanes
was
developed.
In
this
protocol,
various
allenes
were
used
to
afford
the
corresponding
(cyclohexylidene)ethyl
in
moderate
high
yields
good
enantioselectivities.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Aug. 19, 2023
We
report
a
copper-catalyzed
ligand-controlled
selective
1,2-
and
1,4-hydrosilylation
of
1,3-enynes,
which
furnishes
enantiomerically
enriched
propargyl-
1,2-allenylsilane
products
in
high
yields
with
excellent
enantioselectivities
(up
to
99%
ee).
This
reaction
proceeds
under
mild
conditions,
shows
broad
substrate
scope
for
both
1,3-enynes
trihydrosilanes,
displays
regioselectivities.
Mechanistic
studies
based
on
deuterium-labeling
reactions
density
functional
theory
(DFT)
calculations
suggest
that
allenylcopper
is
the
dominant
reactive
intermediate
it
undergoes
metathesis
silanes
via
four-membered
or
six-membered
transition
state,
depending
nature
ligand.
The
weak
interactions
between
ligands
reacting
partners
are
found
be
key
controlling
factor
observed
regioselectivity
switch.
origin
enantiocontrol
also
revealed
by
level
DLPNO-CCSD(T)
calculations.
Green Chemistry,
Journal Year:
2024,
Volume and Issue:
26(5), P. 2592 - 2598
Published: Jan. 1, 2024
A
novel
copper-based
biomass-carbon
aerogel
catalyst
was
prepared
as
a
highly
efficient
and
selective
for
maleimides
reduction
the
first
time
with
excellent
catalytic
activity,
chemo-selectivity,
recyclability.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(9), P. 2204 - 2210
Published: Jan. 1, 2023
An
atom-economical,
regiodivergent
hydrosilylation
reaction
of
isoprene
was
developed
using
an
Earth-abundant
cobalt
catalyst
through
variation
ligands.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 25, 2025
An
efficient
and
straightforward
cobalt-catalyzed
regioselective
intramolecular
hydrosilylation
of
olefins
has
been
developed.
Regioselectivity
is
controlled
by
the
choice
ligands
substrates,
which
operate
through
two
distinct
mechanisms.
This
method
successfully
applied
to
both
terminal
internal
alkenes
phenyl
alkyl
tethers
between
silane
alkene,
demonstrating
its
versatility
across
a
broad
range
substrates.
Chemistry Letters,
Journal Year:
2024,
Volume and Issue:
53(7)
Published: July 1, 2024
Abstract
This
highlight
review
overviews
developments
in
the
synthesis
of
allylsilanes
by
transition
metal–catalyzed
silylation
1,3-dienes
with
disilanes.
We
specifically
disilylation,
which
installs
2
silicon
atoms,
and
silyl-functionalization,
both
another
atom
using
disilanes
reagents
such
as
nucleophiles
electrophiles.
Utilizing
these
methods
for
provides
a
robust
protocol
efficient
desired
1
step,
thereby
streamlining
silyl-functionalization
1,3-dienes.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 11, 2024
Comprehensive
Summary
Arylidenecyclopropanes
(ACPs)
are
highly
strained
substrates
that
can
be
readily
utilized
for
diverse
transformations.
This
study
showcases
the
outcomes
of
copper‐catalyzed
ring‐opening
hydrosilylation
and
hydroboration
reactions
ACPs,
showcasing
precise
cleavage
C—C
bonds.
The
reaction
presents
an
effective
convenient
method
producing
homoallylic
silanes
boronates.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
42(1), P. 13 - 19
Published: Aug. 23, 2023
Comprehensive
Summary
With
the
increasing
demand
for
homoallylic
silanes
and
allylic
silanes,
highly
efficient
regioselective
hydrosilylations
of
conjugated
dienes
are
urgently
needed.
Herein,
we
developed
a
Ni‐catalyzed
regiodivergent
hydrosilylation
aromatic
by
adjusting
temperature
ligands.
Under
low
(–30
°C),
an
eternal‐ligand‐free
system
(Ni/
t
‐BuOK)
can
efficiently
facilitate
3,4‐
anti
‐Markovnikov
to
provide
via
electrophilic
activation
process;
under
room
(25
ligand‐controlled
‐BuOK/PPh
3
)
eventuate
3,4‐Markovnikov
produce
Chalk‐Harrod
process.
Both
systems
compatible
with
various
primary
in
excellent
yields
regioselectivities.
