Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(47)
Опубликована: Авг. 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,
Год журнала:
2024,
Номер
63(20)
Опубликована: Март 4, 2024
Abstract
Dienes
have
been
of
great
interest
to
synthetic
chemists
as
valuable
substrates
due
their
abundance
and
ease
synthesis.
Their
unique
stereoelectronic
properties
enable
broad
reactivity
with
a
wide
range
transition
metals
construct
molecular
complexity
facilitating
synthesis
biologically
active
compounds.
In
addition,
structural
diene
variation
can
result
in
substrate‐controlled
reactions,
providing
mechanistic
insights
into
selectivity
patterns.
The
last
decade
has
seen
wealth
new
methodologies
involving
through
the
power
metal
catalysis.
This
review
summarizes
recent
advances
remaining
opportunities
for
metal‐catalyzed
transformations
dienes.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(14), С. 8150 - 8162
Опубликована: Апрель 4, 2023
Difunctionalization
of
olefins
offers
an
attractive
approach
to
access
complex
chiral
structures.
Reported
herein
is
the
design
N-protected
O-allylhydroxyamines
as
bifunctional
that
undergo
catalytic
asymmetric
1,2-carboamidation
with
three
classes
(hetero)arenes
afford
amino
alcohols
via
C-H
activation.
The
C═C
bond
in
O-allylhydroxyamine
activated
by
intramolecular
electrophilic
amidating
moiety
well
a
migrating
directing
group.
carboamidation
reaction
pattern
depends
on
nature
(hetero)arene
reagent.
Simple
achiral
reacted
give
centrally
β-amino
excellent
enantioselectivity.
employment
axially
prochiral
or
racemic
heteroarenes
afforded
both
axial
and
central
chirality
enantio-
diastereoselectivity.
In
case
heteroarenes,
coupling
follows
kinetic
resolution
s-factor
up
>600.
A
nitrene-based
mechanism
has
been
suggested
based
experimental
studies,
unique
mode
induction
diastereoselectivity
proposed.
Applications
alcohol
products
have
demonstrated.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(33)
Опубликована: Июнь 13, 2023
Abstract
The
difunctionalization
of
unsaturated
bonds
plays
a
vital
role
in
the
enrichment
molecular
complexity.
While
various
catalytic
methods
for
alkene
and
alkyne
have
been
developed
recent
years,
hetero‐functionalization
introduction
two
different
atoms
has
less
explored.
This
is
mainly
due
to
challenges
associated
with
achieving
high
chemo‐,
regio‐,
stereoselectivity,
especially
when
adding
similar
from
same
group
across
bonds.
In
this
study,
we
describe
nickel‐catalyzed,
three‐component
reductive
protocol
14
element
hetero‐difunctionalization
1,3‐enynes
using
electrochemistry.
new
method
mild,
selective,
general,
allowing
silyl‐,
germanyl‐,
stannyl‐alkylation
enynes.
Various
chlorosilanes
as
well
chlorogermans,
chlorostannanes
can
be
successfully
used
combination
aryl/alkyl‐substituted
primary,
secondary,
tertiary
alkyl
bromides
electroreductive
coupling.
Chemical Reviews,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 26, 2024
Cross-electrophile
coupling
(XEC),
defined
by
us
as
the
cross-coupling
of
two
different
σ-electrophiles
that
is
driven
catalyst
reduction,
has
seen
rapid
progression
in
recent
years.
As
such,
this
review
aims
to
summarize
field
from
its
beginnings
up
until
mid-2023
and
provide
comprehensive
coverage
on
synthetic
methods
current
state
mechanistic
understanding.
Chapters
are
split
type
bond
formed,
which
include
C(sp
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.
ACS Catalysis,
Год журнала:
2023,
Номер
13(18), С. 12062 - 12073
Опубликована: Авг. 29, 2023
The
formation
of
silicon–carbon
bonds
through
the
selective
coupling
two
strong
electrophilic
has
been
less
developed.
We
report
here
silylation
reactions
that
proceed
by
Si–Cl/C–O
in
a
process
is
promoted
chromium
catalysis
via
α-agostic
SiH
→
Cr
interactions,
allowing
Si–C
under
ambient
conditions.
occur
inexpensive
hydrochlorosilanes
with
unactivated
aryl
carboxylic
esters
to
give
arylated
hydrosilanes,
while
suppressing
side
hydride-mediated
reduction
achieving
high
chemoselectivity.
In
addition
monosilylation,
both
geminal
Si–Cl
hydrodichlorosilanes
couple
C–O
smoothly
afford
and
achieve
double
silylations.
disilanes
diesters
also
described.
Experimental
theoretical
studies
suggest
initiates
reaction
hydrochlorosilane
Cr,
which
interaction
group
stabilizes
related
intermediate
transition
state,
leading
cleavage
bond
low
barrier
silachromate.
Further
breaking
an
occurs
along
agostic
interaction,
may
serve
as
rate-determining
step
silylation.
observation
normal
second-order
kinetic
isotope
effect
indicates
on
rates
coupling.
Because
reactive
groups
are
retained
silylation,
approach
provides
viable
strategy
access
tetraorganosilane
motifs
late-stage
hydrofunctionalization.
Abstract
Transition
metal‐catalyzed
direct
decarboxylative
transformations
of
aromatic
carboxylic
acids
usually
require
high
temperatures,
which
limit
the
substrate's
scope,
especially
for
late‐stage
applications.
The
development
selective
decarbonylative
acid
derivatives,
most
fundamental
aroyl
chlorides,
with
stable
and
cheap
electrophiles
under
mild
conditions
is
highly
desirable
meaningful,
but
remains
challenging.
Herein,
a
strategy
nickel‐catalyzed
alkylation
chlorides
via
phosphine/nitrogen
ligand
relay
reported.
simple
phosphine
found
essential
decarbonylation
step,
while
nitrogen
promotes
cross‐electrophile
coupling.
Such
system
can
effectively
orderly
carry
out
catalytic
process
at
room
temperature,
utilizing
easily
available
as
an
aryl
electrophile
reductive
alkylation.
This
discovery
provides
new
coupling,
features
operationally
simple,
conditions,
excellent
functional
group
tolerance.
approach
applied
to
methylation
various
pharmaceuticals.
Extensive
experiments
are
carried
provide
insights
into
reaction
pathway
support
process.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(5), С. 2885 - 2894
Опубликована: Фев. 14, 2024
Because
of
their
various
reactivities,
propargyl
acetates
are
refined
chemical
intermediates
that
extensively
applied
in
pharmaceutical
synthesis.
Currently,
reactions
between
and
chlorosilanes
may
be
the
most
effective
method
for
synthesizing
silylallenes.
Nevertheless,
owing
to
adaptability
selectivity
substrates,
transition
metal
catalysis
is
difficult
achieve.
Herein,
nickel-catalyzed
reductive
cross-coupling
substituted
vinyl
synthesis
tetrasubstituted
silylallenes
described.
Therein,
metallic
zinc
a
crucial
reductant
effectively
enables
two
electrophilic
reagents
selectively
construct
C(sp2)–Si
bonds.
Additionally,
Ni-catalyzed
mechanism
involving
radical
process
proposed
on
basis
deuteration-labeled
experiments.
