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.
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
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
25(8), P. 3095 - 3102
Published: Jan. 1, 2023
A
regiodivergent
electrochemical
defluorocarboxylation
of
gem
-difluorocyclopropanes
is
realized,
providing
access
to
branched
and
linear
carboxylated
monofluorinated
alkenes.
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.
Chemical Communications,
Journal Year:
2024,
Volume and Issue:
60(28), P. 3764 - 3773
Published: Jan. 1, 2024
This
feature
article
summarizes
our
efforts
towards
developing
Rh-catalyzed
reactions
of
gem
-difluorinated
cyclopropanes,
briefly
discussing
the
design,
selectivity,
mechanisms
and
future
research
prospects.
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.
Chemical Communications,
Journal Year:
2021,
Volume and Issue:
57(52), P. 6400 - 6403
Published: Jan. 1, 2021
Cu/Pd-Catalyzed
borylfluoroallylation
of
alkenes
with
gem-difluorinated
cyclopropanes
and
B2pin2
was
achieved,
providing
a
modular
general
strategy
for
the
synthesis
monofluoroalkenes.
Synlett,
Journal Year:
2022,
Volume and Issue:
34(01), P. 1 - 13
Published: July 28, 2022
Abstract
As
a
special
class
of
cyclopropanes,
gem-difluorinated
cyclopropanes
have
many
fascinating
properties
as
result
the
gem-difluoro
substitution;
thus,
their
reactions
received
much
attention
from
synthetic
chemistry
community.
Recently,
gradually
emerged
type
novel
and
unique
fluorinated
allylic
synthon
in
cross-coupling
for
synthesis
monofluoroalkenes.
Herein,
we
briefly
summarize
recent
advances
transition-metal-catalyzed
cyclopropanes.
1
Introduction
2
Palladium-Catalyzed
Reactions
with
Linear
Selectivity
3
Branched
4
Other
Metal-Catalyzed
5
Conclusions