Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
366(3), P. 526 - 532
Published: Dec. 21, 2023
Abstract
An
electrochemical
methodology
for
the
construction
of
α
‐CF
3
‐substituted
carbonyl
compounds
in
moderate
to
good
yields
under
exogenous
metal
and
oxidant‐free
conditions
has
been
developed.
The
protocol
involves
single‐electron
oxidation
aryl
ring
generate
a
radical
cation
followed
by
three‐electron
S
N
2
reaction
resulting
formation
substituted
ketones.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(7), P. 2112 - 2133
Published: Jan. 1, 2024
Organofluorine
compounds
are
of
high
value.
NHC-catalyzed
fluorination
and
fluoroalkylation
have
served
as
powerful
versatile
vehicles
for
accessing
the
related
organofluorines.
This
review
focuses
on
recent
developments
in
this
area.
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(32)
Published: June 20, 2023
Direct
synthesis
of
gem-difluorinated
carbocyclic
molecules
represents
a
longstanding
challenge
in
organic
chemistry.
Herein,
Rh-catalyzed
[3+2]
cycloaddition
reaction
between
readily
available
cyclopropanes
(gem-DFCPs)
and
internal
olefins
has
been
developed,
enabling
the
efficient
cyclopentanes
with
good
functional
group
compatibility,
excellent
regioselectivity
diastereoselectivity.
The
resulting
products
can
undergo
downstream
transformations
to
access
various
mono-fluorinated
cyclopentenes
cyclopentanes.
This
demonstrates
use
gem-DFCPs
as
type
"CF2
"
C3
synthon
for
under
transition
metal
catalysis,
which
provides
potential
strategy
synthesizing
other
molecules.
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.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(11)
Published: Jan. 10, 2024
Here
we
present
a
modular,
chemo-,
regio-,
and
stereoselective
synthesis
of
fully-substituted
configuration-defined
alkyl
vinyl
ethers
(AVEs)
using
simple
chemical
feedstocks.
The
distinctive
approach
involves
the
chemo-
regioselective
functionalization
CF
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.
