Chemistry - An Asian Journal,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 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,
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.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Май 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,
Год журнала:
2024,
Номер
15(34), С. 13800 - 13806
Опубликована: Янв. 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
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.
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.
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.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(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.
Organic & Biomolecular Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
In
the
present
study,
mechanism,
origin
of
chemoselectivity,
and
substituent
effects
phosphine-catalyzed
ring-opening
reaction
cyclopropyl
ketone
have
been
investigated
using
DFT
method.
Multiple
pathways,
including
formation
hydrofluorenone,
Cloke-Wilson
product,
cyclopenta-fused
were
studied
compared.
The
computational
results
show
that
pathway
for
hydrofluorenone
is
most
favorable
one,
which
involves
four
processes:
nucleophilic
substitution
to
open
three-membered
ring,
an
intramolecular
Michael
addition
enolate
intermediate,
[1,5]-proton
transfer
give
ylide,
Wittig
deliver
final
product.
For
disclosing
structural
analysis
local
reactivity
index
performed.
Moreover,
also
considered
QTAIM
analysis.
current
study
would
provide
useful
insights
understanding
chemoselective
reactions.
