Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(22)
Опубликована: Март 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,
Год журнала:
2024,
Номер
60(28), С. 3764 - 3773
Опубликована: Янв. 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,
Год журнала:
2024,
Номер
63(23)
Опубликована: Фев. 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.
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.
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,
Год журнала:
2025,
Номер
15(13), С. 10265 - 10272
Опубликована: Янв. 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,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 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.
