Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
42(8), С. 823 - 828
Опубликована: Дек. 8, 2023
Comprehensive
Summary
Herein,
we
report
nickel‐catalyzed
cross‐coupling
of
gem
‐difluorinated
cyclopropanes
with
boronic
acids,
providing
the
corresponding
arylated
2‐fluoroallylic
scaffolds.
This
approach
used
commercially
available
phosphine
ligand
Xantphos
to
obtain
monofluorinated
alkenes
high
regioselectivity
and
Z
‐stereoselectivity.
Mechanistic
studies
proposed
a
Ni(II)‐fluoroallyl
pathway
excluded
radical
pathway.
Meanwhile,
DFT
study
reductive
elimination
clarified
origin
linear
selectivity.
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,
Год журнала:
2023,
Номер
62(23)
Опубликована: Апрель 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,
Год журнала:
2023,
Номер
62(42)
Опубликована: Авг. 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,
Год журнала:
2023,
Номер
25(8), С. 3095 - 3102
Опубликована: Янв. 1, 2023
A
regiodivergent
electrochemical
defluorocarboxylation
of
gem
-difluorocyclopropanes
is
realized,
providing
access
to
branched
and
linear
carboxylated
monofluorinated
alkenes.
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.
Synlett,
Год журнала:
2022,
Номер
34(01), С. 1 - 13
Опубликована: Июль 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
