European Journal of Organic Chemistry,
Год журнала:
2022,
Номер
2022(30)
Опубликована: Июль 8, 2022
Abstract
The
synthesis
of
organoboron
compounds
have
attracted
the
attention
synthetic
community.
In
particular,
molecules
with
C(sp
2
)‐B
bonds
enable
transformation
to
new
C−C
or
C‐heteroatom
by
well‐established
methodologies.
Alkenyl
boronates
possibility
for
further
conversion
boron
moiety
functionalization
double
bond.
This
review
gives
an
overview
on
recent
methodologies
selective
preparation
challenging
highly
substituted
alkenyl
from
alkynes.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(43), С. 23335 - 23341
Опубликована: Авг. 25, 2021
α-Aminosilanes
are
an
important
class
of
organic
compounds
that
show
biological
activity.
In
this
communication,
a
new
approach
to
α-aminosilanes
utilizes
photoredox
catalysis
enable
three-component
coupling
organo(tristrimethylsilyl)silanes
with
feedstock
alkylamines
and
aldehydes
is
presented.
A
wide
range
highly
functionalized
can
be
obtained
in
good
yields
under
mild
conditions.
Both
primary
amines
secondary
compatible
transformation.
Moreover,
optically
pure
accessible
by
using
chiral
amines.
Mechanistic
studies
indicate
reactions
proceed
through
radical/radical
cross-coupling
silyl
radicals
α-amino
alkyl
radicals.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(34), С. 15468 - 15474
Опубликована: Авг. 22, 2022
A
Pd-catalyzed
enantioselective
three-component
reaction
of
N-sulfonylhydrazones,
aryl
bromides,
and
silylboronic
esters
is
developed,
enabling
the
synthesis
chiral
gem-diarylmethine
silanes
in
high
enantioselectivity
with
use
a
newly
identified
Ming-Phos.
Compared
N-tosyl,
more
easily
decomposed
N-mesitylsulfonyl
suitable
as
masking
group
electron-rich
hydrazone
to
improve
efficiency.
The
features
broad
scope
concerning
both
coupling
partners,
enantioselectivity,
mild
conditions.
ready
access
enantiomers
utility
this
catalytic
method
are
also
presented.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(15)
Опубликована: Фев. 7, 2024
Abstract
A
regioselective
silylium‐ion‐promoted
thiosilylation
of
internal
C−C
triple
bonds
with
control
over
the
double
bond
geometry
is
described.
Both
a
C(sp
2
)−S
and
)−Si
are
formed
trans
relationship
in
this
two‐component
reaction
an
alkyne
thiosilane.
The
resulting
orthogonally
functionalized
can
be
chemoselectively
defunctionalized
or
further
processed
by
cross‐coupling
reactions
alkene
configuration
retained.
procedure
also
applicable
to
regio‐
diastereoselective
terminal
allenes
arrive
at
allylic
thioethers
containing
vinylsilane
unit.
These
involve
electrophilic
activation
S−Si
reagent,
both
silylated
thiophenol
even
alkylthiol
derivative,
situ‐generated
carbocation
intermediate.
catalytic
cycle
maintained
bissilylated
aryl‐
alkylsulfonium
ion
as
shuttle
for
cationic
silicon
electrophile.
Its
independent
preparation
structural
characterization
X‐ray
diffraction
reported.
Green Chemistry,
Год журнала:
2024,
Номер
26(8), С. 4785 - 4791
Опубликована: Янв. 1, 2024
We
have
developed
an
efficient
photocatalyzed
arylsilylation
of
alkenes,
utilizing
silylboranes
and
(hetero)aryl
nitriles
in
the
presence
base
photocatalyst.
A
new
mode
of
carbon-carbon
bond
formation
via
electrophilic
activation
a
C-H
has
been
developed
in
the
context
copper-catalyzed
anti-selective
silylative
cyclization
benzylacetylenes
with
silylboronates
for
synthesis
2-silyl-1H-indenes.
The
reaction
proceeds
high
regioselectivity
various
substituted
benzylacetylenes,
and
resulting
products
could
be
further
functionalized.
arene
that
undergoes
acts
as
an
electrophile
release
hydride
under
redox
neutral
conditions,
mechanism
was
probed
by
deuterium-labeling
experiments
density
functional
theory
calculations.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(46), С. 19275 - 19281
Опубликована: Окт. 25, 2021
A
novel
method
for
catalytic
remote
bismetalation
of
alkene
substrates
by
the
addition
dimetal
reagents
is
accomplished
using
chain
walking.
In
presence
a
palladium
catalyst,
reaction
various
1,n-dienes
and
diborons
were
converted
into
cyclopentane
derivatives
with
two
boryl
groups
at
positions
via
facile
regioselective
transformation
an
unactivated
sp3
C-H
bond
to
C-B
bond.
Sequential
construction
three
distant
bonds,
which
difficult
achieve
any
method,
was
reactions
(n
≥
7).
Organic Letters,
Год журнала:
2021,
Номер
23(12), С. 4736 - 4742
Опубликована: Июнь 7, 2021
Unprecedented
copper-catalyzed
regiodivergent
hydrosilylation
reactions
of
substituted
1,3-dienes
with
hydrosilanes
have
been
developed.
The
1,2-
and
1,4-hydrosilylations
1-(hetero)aryl-substituted
were
highly
selectively
controlled
via
variation
the
catalytic
systems.
Meanwhile,
1,4-hydrosilylation
reaction
2-aryl-substituted
diphenylsilane
was
also
successfully
realized
for
first
time.
These
methods
provide
convenient
efficient
approaches
synthesis
structurally
diverse
allylsilanes.
ACS Catalysis,
Год журнала:
2022,
Номер
12(8), С. 4571 - 4580
Опубликована: Апрель 4, 2022
Transition-metal-catalyzed
silicon–carbon
bond
activation
is
one
of
the
most
important
processes
in
both
organosilicon
chemistry
and
homogeneous
catalysis
that
still
rarely
reported
past
decades,
enantioselective
versions
based
on
transition-metal-catalyzed
Si–C
remain
an
ongoing
challenge
asymmetric
catalysis.
Herein,
we
report
a
convenient
cleavage-initiated
[4
+
2]
annulation
benzosilacyclobutenes
with
aldehydes,
which
provides
access
to
direct
synthesis
chiral
six-membered
oxasilacycles
their
derivatives
high
yields
enantioselectivities
(up
97%
ee).
The
catalytic
reaction
proceeds
smoothly
aid
TADDOL-derived
phosphoramidite
ligand
its
Ni
complex
suitable
cavity.
By
switching
work-up
involved,
present
strategy
may
be
extended
subsequent
downstream
transformations
silyl
ether-containing
give
o-tolyl
arylmethanols
ees
quantitative
conversions.
A
series
experimental
results
support
silicon-mediated
organic
controlled
by
nickel
demonstrates
powerful
potential
for
facile
alcohols
drug-like
derivatives.
Finally,
mechanistic
computational
investigations
nickel-catalyzed
offer
insights
into
origin
observed
stereoselective
outcome,
density
functional
theory
calculation
shows
nickel-controlled
Si–C(sp2)
enables
controllable
migratory
insertion
benzaldehyde
Ni–Si
bond,
recognized
as
enantioselectivity-determining
step.
ACS Catalysis,
Год журнала:
2022,
Номер
12(9), С. 4898 - 4905
Опубликована: Апрель 11, 2022
Reductive
functionalization
of
N-heteroarenes
offers
a
route
to
highly
versatile
heterocyclic
synthons
bearing
multiple
transformable
groups.
We
present
herein
the
development
KOtBu-catalyzed
1,2-silaboration
broad
range
N-heteroarenes,
affording
allylamines
or
enamines
with
formation
sp3
C2–Si
bond.
These
labile
compounds
were
isolated
either
as
their
N-acyl
derivatives
rearomatized
2-silyl-N-heteroarenes
by
one-pot
procedures.
A
model
six-membered
ion-pair
complex
was
proposed
rationalize
observed
1,2-regioselectivity,
wherein
KOtBu
catalyst
plays
an
associative
role
in
activating
substrate
and
silylborane
reagent.
Organic Chemistry Frontiers,
Год журнала:
2022,
Номер
9(19), С. 5272 - 5280
Опубликована: Янв. 1, 2022
A
highly
regioselective
silylation
of
unsymmetric
gem
-difluorocyclopropenes
was
achieved
by
the
capture
in-situ
formed
silyl
metal
intermediates,
which
gave
structurally
diverse
silyldifluorocyclopropanes
with
good
yields
and
stereoselectivity.