Synlett,
Год журнала:
2022,
Номер
33(17), С. 1688 - 1694
Опубликована: Июнь 9, 2022
Abstract
As
one
of
the
most
important
indispensable
tools,
organozinc-reagents-based
Negishi
cross-couplings
have
been
extensively
utilized
for
synthesis
biologically
active
molecules
and
feedstock
commodity
chemicals.
However,
use
air-
moisture-sensitive
organozinc
halides
expensive
palladium
catalysis
still
remain
drawbacks.
Recently,
user-friendly
solid
OPiv-supported
C–Zn,
Si–Zn
reagents
with
enhanced
air
moisture
stability
prepared,
which
displayed
superior
reactivity
in
various
transition-metal-catalyzed
cross-couplings,
especially
earth-abundance
cobalt
nickel
catalysis.
Herein,
we
summarized
recent
advances
our
research
work
field
preparation
application
pivalates
present
short
review.
1
Introduction
2
Development
Organozinc
Pivalates
Two-Component
Cross-Couplings
3
Three-Component
4
Conclusion
Outlook
ACS Catalysis,
Год журнала:
2022,
Номер
12(13), С. 7804 - 7810
Опубликована: Июнь 16, 2022
A
visible-light-driven
silyl
radical
generation
method
from
silylboronates
has
been
developed.
The
activation
of
with
a
catalytic
amount
mild
base
promoted
the
single-electron
oxidation
process
to
form
radicals.
Facile
single
electron
transfer
for
borate
readily
occurred
without
hydrogen
atom
hydrosilane
in
presence
various
photoredox
catalysts.
Combining
this
protocol
radical-mediated
N-heterocyclic
carbene
catalysis
enabled
acylsilylation
alkenes
via
relay
generation.
Furthermore,
recent
advanced
methods
synthesis
significantly
improved
utility
process.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(17)
Опубликована: Фев. 18, 2022
Abstract
We
herein
report
the
preparation
of
solid
and
salt‐stabilized
silylzinc
pivalates
from
corresponding
silyllithium
reagents
via
transmetalation
with
Zn(OPiv)
2
.
These
resulting
organosilylzinc
show
enhanced
air
moisture
stability
unique
reactivity
in
silylative
difunctionalization
alkenes.
Thus,
a
practical
chelation‐assisted
nickel‐catalyzed
regioselective
alkyl
benzylsilylation
alkenes
has
been
developed,
which
provides
an
easy
method
to
access
silanes
broad
substrate
scope
wide
functional
group
compatibility.
Kinetic
experiments
highlight
that
OPiv‐coordination
is
crucial
improve
pivalates.
Furthermore,
late‐stage
functionalizations
druglike
molecules
versatile
modifications
products
illustrate
synthetical
utility
this
protocol.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(24), С. 13008 - 13014
Опубликована: Июнь 7, 2023
Transition-metal-catalyzed
sila-cycloaddition
has
been
a
promising
tool
for
accessing
silacarbocycle
derivatives,
but
the
approach
limited
to
selection
of
well-defined
sila-synthons.
Herein,
we
demonstrate
potential
chlorosilanes,
which
are
industrial
feedstock
chemicals,
this
type
reaction
under
reductive
nickel
catalysis.
This
work
extends
scope
coupling
from
carbocycle
synthesis
and
single
C-Si
bond
formation
reactions.
The
proceeds
mild
conditions
shows
good
substrate
functionality
tolerance,
it
offers
new
access
silacyclopent-3-enes
spiro
silacarbocycles.
optical
properties
several
dithienosiloles
as
well
structural
variations
products
demonstrated.
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 4510 - 4522
Опубликована: Март 12, 2024
Organosilicons
are
privileged
skeletons
in
the
domains
of
pharmaceutical
chemistry,
organic
synthesis,
and
materials
science.
Hence,
investigating
catalytic
techniques
for
synthesis
organosilicon
compounds
has
received
a
great
deal
emphasis.
Carbosilylation
alkenes
is
an
efficient
technique
to
introduce
diverse
molecular
architectures
containing
silicon
into
chemical
space.
However,
organohalides
pseudohalides
prerequisites
most
existing
carbosilylation
protocols.
On
other
hand,
utilization
C–H
activation
been
sowing
seeds
successful
development
intricate
scaffolds.
In
this
regard,
synthetic
accessibility
complexed
derivatives
by
through
meta-C–H
approach
remained
intangible.
Herein,
we
present
three-component
strategy
arylsilylation
olefins
with
(het)arenes
silanes
integrating
iron-catalyzed
silyl
radical
generation,
coupled
intrinsic
reactivity
alkene,
ruthenium-catalyzed
functionalization
(het)arene,
leading
targeted
cross-coupled
carbosilylated
product.
addition,
theoretical
investigations
state-of-the-art
dispersion
corrected
density
functional
theory
at
B3PW91-D3/Def2TZVP/CPCM(PhCF3)
shed
intriguing
insights
on
selectivity
probable
mechanistic
pathway
underexplored
cooperative
3d/4d
transition
metal
catalysis,
such
as
formation
its
addition
alkene
catalyzed
iron,
followed
meta-selective
ruthenium
bound
arene,
furnishing
C4
substituted
(het)arene
functionalized
compounds.
Asian Journal of Organic Chemistry,
Год журнала:
2021,
Номер
10(12), С. 3201 - 3232
Опубликована: Ноя. 5, 2021
Abstract
Olefins
are
synthetically
useful
building
blocks
in
modern
organic
synthesis.
Direct
functionalization
of
olefins;
represent
one
the
most
explored
transformations
synthetic
chemistry
due
to
their
easy
availability
and
reactivity
towards
large
number
reactants
affording
diverse
range
compounds.
In
recent
times,
development
new
protocols
for
olefins
is
a
growing
realm.
A
plethora
olefin
methodologies
have
been
reported
literature
through
ionic
free
radical
mechanisms
including
single
electron
transfer
(SET)
last
two
decades.
This
review
gives
an
overview
mono‐
difunctionalization
unactivated
olefins,
with
emphasis
on
mechanistic
details.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(4)
Опубликована: Ноя. 26, 2022
Abstract
Catalytic,
three‐component,
cross‐electrophile
reactions
have
recently
emerged
as
a
promising
tool
for
molecular
diversification,
but
studies
focused
mainly
on
the
alkyl‐carbonations
of
alkenes.
Herein,
scope
this
method
has
been
extended
to
conjugated
dienes
and
silicon
chemistry
through
silylative
difunctionalization
1,3‐dienes
with
chlorosilanes
aryl
bromides.
The
reaction
proceeds
under
mild
conditions
afford
1,2‐linear‐silylated
products,
selectivity
that
is
different
those
obtained
from
conventional
methods
via
an
intermediary
H(C)‐η
3
‐π‐allylmetal
species.
Preliminary
mechanistic
reveal
chlorosilane
reacts
1,3‐diene
first
then
couples
bromide.
Chemical Science,
Год журнала:
2024,
Номер
15(20), С. 7707 - 7713
Опубликована: Янв. 1, 2024
By
leveraging
the
synergistic
interplay
between
nickel
and
photoredox
catalysis,
we
have
developed
a
three-component
silylacylation
strategy
for
various
acrylates,
yielding
valuable
building
blocks
with
carbonyl
silicon
functionalities.
Organic Letters,
Год журнала:
2022,
Номер
24(39), С. 7145 - 7150
Опубликована: Сен. 22, 2022
Herein,
we
report
light-promoted
photo/hydrogen
atom
transfer
dual
catalysis
for
arylsilylation
of
alkenes
via
the
radical-radical
cross-coupling
with
diverse
hydrosilanes,
which
provides
a
simple
and
efficient
method
to
prepare
various
organosilicon
compounds
wide
range
substrate
scope
good
functional
group
tolerance
under
transition-metal-
chemical-oxidant-free
conditions.
Furthermore,
can
also
proceed
possible
electron
donor-acceptor
complex
exogenous
photocatalyst-free
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Март 16, 2022
Abstract
π-Extended
tetrasubstituted
olefins
are
widely
found
motifs
in
natural
products,
leading
drugs,
and
agrochemicals.
Thus,
development
of
modular
strategies
for
the
synthesis
complex
all-carbon-substituted
always
draws
attention.
The
difunctionalization
unsymmetrical
alkynes
is
an
attractive
approach
but
it
has
remained
faced
with
regioselectivity
issues.
Here
we
report
discovery
a
regio-
stereoselective
syn
-1,2-dicarbofunctionalization
internal
alkynes.
A
cationic
Pd-catalyzed
three-component
coupling
aryl
diazonium
salts,
boronic
acids
(or
olefins)
yne-acetates
enables
access
to
all-carbon
substituted
olefins.
transformation
features
broad
scope
labile
functional
group
tolerance,
building
chemical
space
structural
diversity
(94
molecules).
value
this
synthetic
method
demonstrated
by
direct
products
drug
candidates
containing
yne-acetates,
enable
highly
structurally
allyl
acetate
analogues
biologically
important
compounds.
Synthetic
versatility
carboxylate
bearing
also
presented.
reaction
outcome
attributed
situ
formation
stabilized
aryl-Pd
species,
which
regulates
regioselective
aryl-palladation
yne-acetates.
Control
experiments
reveal
synergy
between
protecting
Pd-intermediate
productivity;
density
theory
(DFT)
studies
rationalize
selectivity
reaction.
