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.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(20)
Published: Jan. 25, 2024
C-F
Insertion
reactions,
where
an
organic
fragment
formally
inserts
into
a
carbon-fluorine
bond
in
substrate,
are
highly
attractive,
yet
largely
unexplored,
methods
to
prepare
valuable
fluorinated
molecules.
The
inherent
strength
of
bonds
and
the
resulting
need
for
large
thermodynamic
driving
force
initiate
cleavage
often
leads
sequestering
released
fluoride
unreactive
by-product.
Recently,
however,
several
groups
have
succeeded
overcoming
this
challenge,
opening
up
study
insertion
as
efficient
atom-economical
approach
compounds.
In
article,
recent
breakthroughs
discussed
focusing
on
key
conceptual
advances
that
allowed
both
subsequent
incorporation
product.
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.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 6, 2025
The
unique
properties
of
fluorinated
organic
compounds
have
received
intense
interest
and
conquered
a
myriad
applications
in
the
chemical
pharmaceutical
sciences.
Today,
an
impressive
range
alkyl
fluorides
are
commercially
available,
there
many
practical
methods
to
make
them
exist.
However,
unmatched
stability
inertness
C–F
bond
largely
limited
its
synthetic
value,
which
is
very
different
from
widely
accepted
utility
chlorides,
bromides,
iodides
that
serve
everyday
as
"workhorse"
building
blocks
countless
carbon–carbon
forming
reactions.
This
study
demonstrates
high-yielding
functionalization
under
mild
conditions,
i.e.,
at
temperatures
low
−78
°C,
short
reaction
times
with
unconventional
chemoselectivity.
Cryogenic
Csp3–F
cleavage
using
fluorophilic
organoaluminum
together
fast
nucleophile
transfer
intermediate
ate
complexes
forge
bonds
unactivated
primary,
secondary,
tertiary
alike.
method,
exploits
Al–F
thermodynamic
driving
force,
highly
selective
toward
functionalization,
whereas
other
functional
groups
including
chloride,
bromide,
iodide,
aryl
halide,
alkenyl,
alkynyl,
difluoroalkyl,
trifluoromethyl,
ether,
ester,
hydroxyl,
acetal,
heteroaryl,
nitrile,
nitro,
amide
tolerated,
unexpected
reversal
long-standing
main
group
organometallic
halide
cross-coupling
reactivity
compatibility
patterns.
As
result,
strongest
single
chemistry
can
now
be
selectively
targeted
arylation,
alkylation,
alkenylation,
alkynylation
reactions
used
late-stage
complementary
currently
available
methods.
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.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 18, 2025
We
report
an
efficient
palladium-catalyzed
ring-opening
defluorinative
Hiyama
cross-coupling
of
gem-difluorocyclopropanes
with
structurally
diverse
(hetero)arylsilanes
through
C-C
bond
activation
and
C-F
cleavage.
This
regioselective
features
a
broad
substrate
scope
excellent
functional
group
compatibility,
affording
variety
linear
2-fluoroallylic
scaffolds
in
good
yields
high
Z-selectivity.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(8), P. 5442 - 5457
Published: April 3, 2024
In
this
study,
concise,
efficient,
and
modular
hydrophosphinylation
hydroamidation
of
gem-difluorocyclopropenes
were
disclosed
in
a
mild
transition-metal-free
pattern.
Through
approach,
phosphorus,
nitrogen-containing
gem-difluorocyclopropanes
produced
moderate
to
good
yields
with
excellent
regio-
diastereoselectivity.
Readily
available
nucleophilic
reagents,
along
inexpensive
inorganic
bases,
employed.
Multiple
synthetic
applications,
including
gram-scale
derivatization
reactions
modification
bioactive
molecules,
subsequently
elaborated.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(15), P. 3387 - 3396
Published: July 23, 2024
Abstract
We
herein
describe
a
method
in
the
synthesis
of
aryl
ether
derivatives
from
cross‐coupling
reaction
vinylidenecyclopropane‐diesters
(VDCP‐diesters)
with
commercially
available
phenolic
compounds
for
formation
C−O
bond
under
palladium
catalysis
and
assisted
by
Sc(OTf)
3
/Cs
2
CO
.
This
developed
transformation
proceeds
through
nucleophilic
addition
at
2‐position
allenic
moiety
50
°C
4.0
h
is
compatible
substituents
such
as
bromine,
iodine
borate
on
substrates
via
zwitterionic
π‐propargyl
species,
affording
desired
products
29%
to
95%
isolated
yields.
A
plausible
mechanism
has
been
also
proposed
basis
control,
deuterium
labeling
experiments
density
functional
theory
(DFT)
calculations.
