Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(42), P. 12419 - 12425
Published: Jan. 1, 2022
The
control
of
linear/branched
selectivity
is
one
the
major
focuses
in
transition-metal
catalyzed
allyl-allyl
cross-coupling
reactions,
which
bond
connection
occurs
at
terminal
site
both
allyl
fragments
forming
different
types
1,5-dienes.
Herein,
terminal/internal
regioselectivity
investigated
and
found
to
be
switchable
reactions
between
gem-difluorinated
cyclopropanes
allylboronates.
controlled
arises
from
fine-tuning
rhodium
catalytic
system.
Fluorinated
1,3-dienes,
1,4-dienes
1,5-dienes
are
therefore
produced
good
yields
with
respectively
isomerized
terminal,
internal,
regioselectivity.
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.
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:
2020,
Volume and Issue:
57(10), P. 1262 - 1265
Published: Dec. 22, 2020
A
palladium-catalyzed
allylic
alkylation
dearomatization
of
β-naphthols
and
indoles
withgem-difluorinated
cyclopropanes
has
been
developed
for
the
first
time.
The Journal of Organic Chemistry,
Journal Year:
2019,
Volume and Issue:
84(21), P. 13646 - 13654
Published: Sept. 20, 2019
A
Pd-catalyzed
ring-opening
sulfonylation
of
gem-difluorocyclopropanes
is
reported.
This
protocol
involves
C–C
bond
cleavage,
β-F
elimination,
and
allylic
coupling
to
form
corresponding
2-fluoroallylic
sulfones
efficiently
with
Z-selectivity.
Different
substrates
bearing
diverse
functional
groups
are
tolerated.
Moreover,
this
method
successfully
used
for
the
late-stage
derivation
several
bioactive
molecules.
Organic Letters,
Journal Year:
2020,
Volume and Issue:
22(21), P. 8681 - 8686
Published: Oct. 28, 2020
A
strategically
novel
protocol
for
ring-opening
functionalization
of
aryl
gem-difluorocyclopropanes
(F2CPs),
which
allows
an
expedient
construction
CF3-containing
architectures
via
visible-light-promoted
F-nucleophilic
attack
manifold,
was
disclosed.
Single
electron
oxidation
F2CPs
ascribed
as
the
critical
step
success
this
transformation
by
prompting
attack,
well
ensuing
C–C
bond
scission.
The
observed
intriguing
regioselectivity
fluoroincorporation
in
reaction
rationalized
invoking
cation-stabilization
property
gem-difluorine
substituents
and
also
thermodynamic
gains
acquired
from
forming
CF3
functionality.
By
using
cost-effective
fluorination
reagent
readily
available
substrates,
a
broad
collection
structurally
diversified
α-allyl-β-trifluoromethyl
ethylbenzene
derivatives
could
be
obtained
generally
good
yields.
Further
mechanistic
investigations
proved
engagement
benzylic
radical
intermediate
transformation.
