Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(22)
Published: March 22, 2024
Abstract
The
use
of
gem
‐difluorinated
cyclopropanes
(
‐DFCPs)
as
fluoroallyl
surrogates
under
transition‐metal
catalysis
has
drawn
considerable
attention
recently
but
such
reactions
are
restricted
to
producing
achiral
or
racemic
mono‐fluoroalkenes.
Herein,
we
report
the
first
enantioselective
allylation
indoles
rhodium
with
‐DFCPs.
This
reaction
shows
exceptional
branched
regioselectivity
towards
‐DFCPs,
which
provides
an
efficient
route
enantioenriched
fluoroallylated
wide
substrate
scope
and
good
functional
group
tolerance.
Inorganic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 3, 2024
Inspired
by
the
intriguing
nature
of
metal-π
interaction
in
organometallic
chemistry,
a
novel
1D
hybrid
material
has
been
designed.
Herein,
functionalized
tellurium
allyl
macrocycle
(TAM)
acts
as
molecular
building
block
and
is
knit
together
via
silver-π
to
obtain
Ag-TAM.
Ag
coordinated
two
groups
phenyl
ring
η2
mode.
Instead
conventional
polymerization
strategy,
employed
interlink
macrocycles.
TAM
Ag-TAM
showed
electrocatalytic
capability
for
conversion
nitrate
ammonia.
an
NH3
yield
rate
2-fold
greater
than
with
high
faradaic
efficiency
94.6%
good
durability,
proving
that
interlinking
macrocycles
improves
catalytic
activity.
Detailed
periodic
density
functional
theory
(DFT)
calculations
unveil
mechanistic
insights,
suggesting
cooperative
catalysis
between
neighboring
sites
contributing
enhanced
efficiency.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
42(8), P. 823 - 828
Published: Dec. 8, 2023
Comprehensive
Summary
Herein,
we
report
nickel‐catalyzed
cross‐coupling
of
gem
‐difluorinated
cyclopropanes
with
boronic
acids,
providing
the
corresponding
arylated
2‐fluoroallylic
scaffolds.
This
approach
used
commercially
available
phosphine
ligand
Xantphos
to
obtain
monofluorinated
alkenes
high
regioselectivity
and
Z
‐stereoselectivity.
Mechanistic
studies
proposed
a
Ni(II)‐fluoroallyl
pathway
excluded
radical
pathway.
Meanwhile,
DFT
study
reductive
elimination
clarified
origin
linear
selectivity.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(11)
Published: Jan. 10, 2024
Abstract
Here
we
present
a
modular,
chemo‐,
regio‐,
and
stereoselective
synthesis
of
fully‐substituted
configuration‐defined
alkyl
vinyl
ethers
(AVEs)
using
simple
chemical
feedstocks.
The
distinctive
approach
involves
the
chemo‐
regioselective
functionalization
CF
2
unit
in
gem
‐difluorinated
cyclopropanes
with
O−H
C−H
nucleophiles
specific
order.
resulting
highly
functionalized
cyclopropanyl
then
undergo
ring‐opening
process
to
produce
AVEs.
These
AVEs
are
rarely
accessible
through
conventional
methods
easily
transformable.
Mechanistic
experiments
indicate
that
success
this
method
relies
on
use
dual‐functional
copper
catalysis,
which
is
involved
both
subsequent
process.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(22)
Published: March 22, 2024
Abstract
The
use
of
gem
‐difluorinated
cyclopropanes
(
‐DFCPs)
as
fluoroallyl
surrogates
under
transition‐metal
catalysis
has
drawn
considerable
attention
recently
but
such
reactions
are
restricted
to
producing
achiral
or
racemic
mono‐fluoroalkenes.
Herein,
we
report
the
first
enantioselective
allylation
indoles
rhodium
with
‐DFCPs.
This
reaction
shows
exceptional
branched
regioselectivity
towards
‐DFCPs,
which
provides
an
efficient
route
enantioenriched
fluoroallylated
wide
substrate
scope
and
good
functional
group
tolerance.
