Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(50), P. 9020 - 9024
Published: Dec. 8, 2023
This
study
presents
a
novel
method
for
the
regioselective
coupling
of
gem-difluorinated
cyclopropanes
with
gem-diborylmethane,
utilizing
Pd-catalyst
system.
innovative
approach
enables
synthesis
2-fluoroalkenyl
monoboronate
scaffolds
high
Z-selectivity.
The
resulting
products
undergo
further
transformations,
including
oxidation,
Suzuki
cross-coupling,
and
trifluoroborylation,
all
which
are
achieved
good
yields.
work
introduces
valuable
synthetic
pathway
to
access
important
fluorinated
compounds
various
applications
in
organic
chemistry.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(28), P. 5051 - 5055
Published: July 14, 2022
A
new
Co-catalyzed
sequential
C-C
and
C-F
activation
of
gem-difluorinated
cyclopropanes
(gem-FCPs)
to
form
nucleophilic
fluoroallylcobalt,
followed
by
addition
aldehydes,
is
reported.
The
protocol
features
the
regioselective
cleavage
dual
chemical
bonds
readily
available
gem-FCPs
prepare
easily
separable
linear
(Z)-
(E)-fluorinated
homoallylic
alcohols
with
a
broad
scope.
This
discovery
established
strategy
for
efficient
transformation
as
well
synthesis
challenging
fluorinated
alcohols.
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(42), P. 12419 - 12425
Published: Jan. 1, 2022
The
control
of
linear/branched
selectivity
is
one
the
major
focuses
in
transition-metal
catalyzed
allyl-allyl
cross-coupling
reactions,
which
bond
connection
occurs
at
terminal
site
both
allyl
fragments
forming
different
types
1,5-dienes.
Herein,
terminal/internal
regioselectivity
investigated
and
found
to
be
switchable
reactions
between
gem-difluorinated
cyclopropanes
allylboronates.
controlled
arises
from
fine-tuning
rhodium
catalytic
system.
Fluorinated
1,3-dienes,
1,4-dienes
1,5-dienes
are
therefore
produced
good
yields
with
respectively
isomerized
terminal,
internal,
regioselectivity.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(6), P. 3787 - 3793
Published: Feb. 24, 2023
Fluorinated
compounds
have
found
widespread
applications
in
pharmaceuticals,
agrochemicals,
and
materials
science.
Precise
construction
of
α-difluoromethylene
ether
(CF2-O)
moiety
organic
molecules
is
high
demand.
Herein,
a
visible
light-promoted
reaction
protocol
for
the
synthesis
from
gem-difluorocyclopropane
described.
The
key
ring-opening
step
induced
by
hyperconjugative
interaction
cyclopropane
with
photo-oxidized
aromatic
rings.
This
easy
scale-up,
products
bearing
synthetic
handle
enable
their
further
manipulation.
Advanced Science,
Journal Year:
2024,
Volume and Issue:
11(18)
Published: March 9, 2024
Abstract
Transition‐metal
(TM)
catalyzed
reaction
of
gem
‐difluorinated
cyclopropanes
(
‐DFCPs)
has
drawn
much
attention
recently.
The
generally
occurs
via
the
activation
distal
C─C
bond
in
‐DFCPs
by
a
low‐valent
TM
through
oxidative
addition,
eventually
producing
mono‐fluoro
olefins
as
coupling
products.
However,
achieving
regioselective
proximal
that
overcomes
intrinsic
reactivity
catalysis
remains
elusive.
Here,
new
mode
enabled
high‐valent
copper
catalysis,
which
allows
exclusive
congested
is
presented.
achieves
fluoroarylation
uses
NFSI
(N‐fluorobenzenesulfonimide)
electrophilic
fluoro
reagent
and
arenes
C─H
nucleophiles,
enabling
synthesis
diverse
CF
3
‐containing
scaffolds.
It
proposed
species
plays
an
important
role
possibly
σ‐bond
metathesis.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(50), P. 9020 - 9024
Published: Dec. 8, 2023
This
study
presents
a
novel
method
for
the
regioselective
coupling
of
gem-difluorinated
cyclopropanes
with
gem-diborylmethane,
utilizing
Pd-catalyst
system.
innovative
approach
enables
synthesis
2-fluoroalkenyl
monoboronate
scaffolds
high
Z-selectivity.
The
resulting
products
undergo
further
transformations,
including
oxidation,
Suzuki
cross-coupling,
and
trifluoroborylation,
all
which
are
achieved
good
yields.
work
introduces
valuable
synthetic
pathway
to
access
important
fluorinated
compounds
various
applications
in
organic
chemistry.
