Chemistry - An Asian Journal,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 18, 2024
Abstract
A
photopromoted
Pd‐catalyzed
Heck
reaction
of
gem
‐difluorocyclopropyl
bromides
(DFCBs)
with
styrenes
to
deliver
vinyl
‐difluorinated
cyclopropanes
(VDFCs)
under
mild
conditions
has
been
developed.
The
demonstrates
good
functional
group
compatibility
while
providing
high
E/Z
ratio
the
products.
Furthermore,
desired
VDFCs
can
be
easily
transformed
into
fluorinated
cyclic/acyclic
architectures,
which
may
broaden
its
applications
in
organic
synthesis.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(23)
Published: April 2, 2024
The
diversified
synthesis
of
chiral
fluorinated
cyclobutane
derivatives
has
remained
a
difficult
task
in
synthetic
chemistry.
Herein,
we
present
an
approach
for
asymmetric
hydroboration
and
formal
hydrodefluorination
gem-difluorinated
cyclobutenes
through
rhodium
catalysis,
providing
α-boryl
cyclobutanes
monofluorinated
with
excellent
regio-
enantioselectivity,
respectively.
key
to
the
success
two
transformations
relies
on
efficient,
mild
highly
selective
rhodium-catalyzed
HBPin
(pinacolborane),
which
subsequent
addition
base,
catalytic
amount
palladium
some
cases,
results
formation
products
four-membered
ring
retained.
obtained
are
versatile
building
blocks
that
provide
platform
enantioenriched
great
diversity.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: May 21, 2024
Abstract
Transition-metal
catalyzed
allylic
substitution
reactions
of
alkenes
are
among
the
most
efficient
methods
for
synthesizing
diene
compounds,
driven
by
inherent
preference
an
inner-sphere
mechanism.
Here,
we
present
a
demonstration
outer-sphere
mechanism
in
Rh-catalyzed
reaction
simple
using
gem
-difluorinated
cyclopropanes
as
allyl
surrogates.
This
unconventional
offers
opportunity
fluorine
recycling
via
C
−
F
bond
cleavage/reformation,
ultimately
delivering
carbofluorination
products.
The
developed
method
tolerates
wide
range
alkenes,
providing
access
to
secondary,
tertiary
fluorides
and
-difluorides
with
100%
atom
economy.
DFT
calculations
reveal
that
formation
goes
through
unusual
nucleophilic
allyl-Rh
species
instead
migration
insertion,
generated
carbon
cation
then
forms
tetrafluoroborate
fluoride
shuttle.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(34), P. 13800 - 13806
Published: Jan. 1, 2024
Metathesis
reactions
have
been
established
as
a
powerful
tool
in
organic
synthesis.
While
great
advances
were
achieved
double-bond
metathesis,
like
olefin
metathesis
and
carbonyl
single-bond
has
received
less
attention
the
past
decade.
Herein,
we
describe
first
C(sp
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(32), P. 6905 - 6909
Published: Aug. 1, 2024
We
present
a
palladium-catalyzed
ring-opening
reaction
that
induces
indoles
to
cross-couple
with
gem-difluorocyclopropanes.
The
proceeds
through
domino
process
of
C–C
bond
activation
and
C–F
elimination,
followed
by
C–C(sp2)
coupling
produce
various
2-fluoroallylindoles.
This
method
is
characterized
its
high
functional
group
tolerance,
good
yields
regioselectivity,
under
base-free
conditions.
synthetic
utility
the
products
illustrated
functionalization
NH
C2
positions
indole
scaffold.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 21, 2025
We
present
a
Pd-IPent-catalyzed
ring-opening
defluorinative
annulation
reaction
of
gem-difluorocyclopropanes
with
enamides,
which
provides
convenient
and
efficient
strategy
for
the
synthesis
multisubstituted
N-H
pyrrole
derivatives.
This
transformation
selectively
cleaves
C1-C3
bond,
two
C-F
bonds,
C-N
bond
in
one-pot
procedure.
Additionally,
this
protocol
allows
modification
several
bioactive
molecules.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 26, 2025
We
herein
report
the
development
of
a
novel
Pd-catalyzed
dearomative
functionalization
pyrroles
with
gem-difluorinated
cyclopropanes
(gem-F2CPs).
This
dearomative/ring-opening
strategy
streamlines
diversity-oriented
synthesis
(DOS)
α-quaternary
2-fluoroallylic
2H-pyrroles
broad
scope
and
excellent
functional
group
tolerance,
which
enables
efficient
late-stage
transformation
complex
bioactive
molecule-derived
gem-F2CPs.
Derivation
resulting
fluoroallylic
to
different
synthetically
useful
2H-pyrrole
motifs
demonstrated
synthetic
value
this
methodology.
RSC Advances,
Journal Year:
2025,
Volume and Issue:
15(13), P. 10265 - 10272
Published: Jan. 1, 2025
This
study
introduces
an
efficacious
palladium-catalyzed
method
for
the
regioselective
and
stereoselective
cross-coupling
of
gem
-difluorinated
cyclopropanes
with
array
-diborylalkanes
under
mild
reaction
conditions.
