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.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(11), P. 2093 - 2098
Published: March 11, 2022
Palladium-catalyzed
synthesis
of
3-acyl
and
-allyl
indoles
has
been
realized
by
merging
nucleophilic
cyclization
ortho-alkynylanilines
with
ring
opening
three-membered
rings
such
as
cyclopropenones
gem-difluorinated
cyclopropanes.
These
functionalized
were
obtained
in
moderate
to
high
yields
stereoselectivity
both
cases.
This
protocol
provides
an
alternative
method
toward
under
mild
redox-neutral
conditions.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(11), P. 6495 - 6505
Published: May 17, 2022
Controlling
the
selectivity
of
synthetically
useful
reactions
has
been
a
longstanding
objective
organic
chemistry.
We
report
regiodivergent
synthetic
protocol
allowing
access
to
diverse
fluorinated
1,5-dienes
through
Pd/NHC-catalyzed
ring-opening
allylation
gem-difluorocyclopropanes.
Density
functional
theory
(DFT)
calculations
on
regioselectivity-determining
transition
states
provided
critical
insight
into
design
NHC
ligand
for
switching
regioselectivity.
Consistent
with
DFT
predictions,
N-heterocyclic
carbene
(NHC)
ligands
bulky
ortho
substituents
favored
branched
allylation,
IHept
providing
>
20:1
branched/linear
less
hindered
such
as
IMes
thermodynamically
more
stable
linear
products.
were
able
carry
out
late-stage
modification
various
complex
molecules
using
this
protocol.
Our
ligand-controlled
approach
provides
efficient
regioisomeric
from
same
starting
materials
and
constitutes
valuable
addition
toolbox
diversity-oriented
synthesis.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(15), P. 8857 - 8867
Published: July 10, 2022
The
unique
properties
of
the
fluorine-containing
compounds
and
their
widespread
applications
raise
demand
for
dependable
synthetic
methods
on
precise
introduction
substituents
into
organic
molecules.
Herein,
a
site-divergent
fluoroallylation
olefins
that
can
incorporate
fluoroallyl
motif
different
alkenyl
C–H
sites
is
disclosed.
gem-Difluorinated
cyclopropanes
are
employed
as
sources
via
rhodium-catalyzed
C–C
bond
activation.
This
strategy
provide
two
regioisomeric
fluorinated
skipped
dienes
in
good
yields
with
excellent
site-selectivity.
resulting
products
serve
useful
building
blocks
to
access
various
molecules
isosteric
β,
γ-unsaturated
amides,
which
promising
be
exploited
medicinal
chemistry.
Mechanistic
studies
revealed
electronic
property
rhodium
catalysts
crucial
controllable
site-selectivity,
providing
more
insights
beyond
methodology
tuning
selectivity
metal
catalysts.
ChemCatChem,
Journal Year:
2022,
Volume and Issue:
14(24)
Published: Aug. 11, 2022
Abstract
gem
‐Difluorocyclopropanes
(F
2
CPs)
have
aroused
considerable
attention
not
only
from
the
structural
perspective
but
also
due
to
their
ability
participate
in
various
valuable
transformations.
This
Review
summarizes
advances
catalytic
ring‐opening
reactions
of
‐F
CPs,
especially
emphasizing
reactivities
and
applications
those
non‐activated
ones
under
transition‐metal
catalysis.
Their
achievements,
synthetic
limitations
are
discussed
with
aim
stimulate
enthusiasm
for
further
development.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(23)
Published: April 4, 2023
Defluorinative
manipulation
of
polyfluorinated
molecules
has
shown
great
promise
due
to
its
granting
synthetic
versatility
inert
C-F
bonds.
The
development
chemo-,
stereo-
and
regioselective
strategies
realize
highly
efficient
formation
either
the
linear/branched
or
E/Z
products
from
gem-difluorocyclopropanes
(gem-F2
CPs)
is
a
challenging
task.
Herein,
we
have
realized
palladium/NHC-catalyzed
fluoroallylation/annulation
hydrazones
with
gem-F2
CPs
that
incorporate
hydrazone
N2
moiety
into
products.
thermodynamically
unstable
fluorinated
E-allylation
aryl
ketone
were
obtained
for
first
time,
while
di-alkyl
yielded
monofluorinated
branched
selectivity
under
similar
reaction
conditions.
With
aldehyde
hydrazones,
two
kinds
pyrazoles
via
defluorinative
allylation/annulation
cascade,
in
which
different
carbon
atoms
could
be
incorporated
pyrazole
rings
regiospecifically.
DFT
calculations
revealed
divergent
was
kinetically
controlled
final
C-C
bond
proceeded
through
7-membered
TS.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(42)
Published: Aug. 12, 2023
Abstract
An
unprecedented
Pd‐catalyzed
fluorinative
bifunctionalization
of
aziridines
and
azetidines
was
successfully
developed
via
regioselective
C−C
C−F
bond
cleavage
gem‐difluorocyclopropanes,
leading
to
various
β,β′‐bisfluorinated
amines
β,γ‐bisfluorinated
amines.
This
reaction
achieved
by
incorporating
a
2‐fluorinated
allyl
group
fluorine
atom
scissored
from
gem‐difluorocyclopropane
in
100
%
economy
for
the
first
time.
The
mechanistic
investigations
indicated
that
underwent
amine
attacking
palladium
complex
generate
η
2
‐coordinated
N‐allyl
aziridine
followed
fluoride
ligand
transfer
affording
final
β‐
γ‐fluorinated
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(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.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(23)
Published: Feb. 27, 2024
A
novel
enantioselective
Tsuji-Trost-type
cross
coupling
reaction
between
gem-difluorinated
cyclopropanes
and
N-unprotected
amino
acid
esters
enabled
by
synergistic
Pd/Ni/chiral
aldehyde
catalysis
is
presented
herein.
This
transformation
streamlined
the
diversity-oriented
synthesis
(DOS)
of
optically
active
α-quaternary
α-amino
bearing
a
linear
2-fluoroallylic
motif,
which
served
as
an
appealing
platform
for
construction
other
valuable
enantioenriched
compounds.
The
key
intermediates
were
confirmed
HRMS
detection,
while
DFT
calculations
revealed
that
excellent
enantioselectivity
was
attributed
to
stabilizing
non-covalent
interactions
Pd(II)-π-fluoroallyl
species
Ni(II)-Schiff
base
complex.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(14), P. 3974 - 3981
Published: Jan. 1, 2024
A
defluorinative
cyclization
of
readily
available
trifluoromethyl
enones
with
phosphine
oxides
for
the
synthesis
polysubstituted
furans
is
developed
in
a
pure
water
solution.
