The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(14), P. 10299 - 10310
Published: July 2, 2024
A
three-component
strategy
was
developed
to
enable
hydrodefluoroamination
of
β-trifluoromethyl
enones
by
selectively
activating
two
C(sp3)-F
bonds
in
the
trifluoromethyl
group.
The
method
involved
a
sequence
carbonyl
reduction,
hydrodefluorination,
and
defluoroamination
under
transition-metal-free
conditions.
Synthetically
useful
(E)-stereospecific
α-fluoroenamides
were
obtained
good
yields
with
diverse
functional
group
tolerance,
which
could
be
easily
transformed
into
valuable
organofluorides
heterocycles.
auxiliary
exerts
both
electronic
steric
impacts
on
CF3-alkenes,
allowing
for
controllable
selective
defluorination.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(14), P. 3974 - 3981
Published: Jan. 1, 2024
A
defluorinative
cyclization
of
readily
available
trifluoromethyl
enones
with
phosphine
oxides
for
the
synthesis
polysubstituted
furans
is
developed
in
a
pure
water
solution.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 24, 2024
A
three-component
reaction
of
trifluoromethyl
enones,
phosphine
oxides,
and
alcohols
in
water
solution
is
developed.
This
defluorinative
occurs
through
a
cascade
process
involving
defluorophosphorylation,
defluoroalkyloxylation,
defluoroheteroannulation,
enabling
the
modular
synthesis
furans
with
four
distinct
substituents:
C2-alkyloxy,
C3-trifluoromethyl,
C4-phosphoryl,
C5-(hetero)aryl
groups.
Moreover,
apart
from
alcohol
substrates,
scope
nucleophiles
could
be
further
extended
to
phenols,
azacycles,
or
sulfonamide.
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
25(23), P. 9672 - 9679
Published: Jan. 1, 2023
A
H
2
O-promoted
and
(NH
4
)
CO
3
-enabled
defluoroiminization
reaction
of
fluoroalkyl
alkenes
for
the
synthesis
fluoroalkylated
1,5-diazapentadienes
has
been
developed.
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
25(16), P. 6489 - 6497
Published: Jan. 1, 2023
An
efficient
“on-water”
reaction
of
β-trifluoromethylated
enones
with
phosphine
oxides
was
developed
for
the
preparation
phosphorylated
gem
-difluorodienes
excellent
Z
-selectivity.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(42), P. 7595 - 7600
Published: Oct. 13, 2023
O-Phosphination
of
α-dicarbonyls
via
sequential
in
situ
formation
a
Kukhtin-Ramirez
adduct
and
P(NMe2)3-catalyzed
process
has
been
exploited
for
the
synthesis
α-phosphoryloxy
carbonyls.
A
range
P(O)-H
derivatives,
including
diarylphosphine
oxides,
arylphosphinates,
phosphinates,
are
competent
candidates
to
be
introduced
into
this
transformation,
various
carbonyls
obtained.
This
approach
possesses
advantages
mild
conditions,
simple
operations,
atom
economy,
high
efficiency,
gram-scale
synthesis,
which
make
it
promising
toolbox.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(18), P. 5144 - 5150
Published: Jan. 1, 2024
A
transition-metal-free
multi-functionalization
reaction
of
β-trifluoromethyl
enones
and
azacycles
is
first
developed
for
the
synthesis
valuable
amino-2,3-dihydrofuran
derivatives.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(34), P. 6368 - 6373
Published: Aug. 18, 2023
A
chemo-,
regio-,
and
stereoselective
reaction
of
trifluoromethyl
enones,
phenylsilane,
phosphine
oxides
through
a
sequential
hydrodefluorination
defluorophosphorylation
relay
is
developed
for
the
synthesis
distinctive
gem-fluorophosphine
alkenes.
This
multicomponent
occurred
under
transition-metal-free
conditions
with
good
functional
group
tolerance.
Moreover,
preinstalled
carbonyl
auxiliary
important
tuning
reactivity
β-trifluoromethyl
thereby
enabling
controllable
selective
functionalization
two
fluorine
atoms
in
trifluoromethylated
enones.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(24), P. 17284 - 17296
Published: Dec. 6, 2023
The
selective
functionalization
of
trifluoromethyl
groups
through
C-F
cleavage
poses
a
significant
challenge
due
to
the
high
bond
energy
C(sp3)-F
bonds.
Herein,
we
present
dihydroacridine
derivatives
as
photocatalysts
that
can
functionalize
with
various
alkenes
under
mild
conditions.
Mechanistic
studies
and
DFT
calculations
revealed
upon
irradiation,
exhibit
reducibility
function
for
reductive
defluorination.
This
process
involves
sequential
single-electron
transfer
mechanism.
research
provides
valuable
insights
into
properties
photocatalysts,
highlighting
importance
maintaining
planar
conformation
large
conjugated
system
optimal
catalytic
activity.
These
findings
facilitate
efficient
reduction
inert
chemical
Organic Letters,
Journal Year:
2025,
Volume and Issue:
27(10), P. 2492 - 2497
Published: March 5, 2025
A
controlled
cleavage
of
double
C-F
bonds
in
sterically
hindered
tetrasubstituted
CF3-alkenes
using
formate
salt
has
been
achieved
through
a
photoinduced
electron
transfer
approach.
Diverse
γ-branched
multifunctionalized
gem-difluoroalkenes
and
α-fluoroacrylic
acids
are
obtained
sequentially
via
hydrodefluorination
bond
carboxylation
with
good-to-high
yields.
Precisely
controlling
the
quantity
reaction
time
is
crucial
for
obtaining
divergent
defluorinative
products.
Formate
serves
as
C1
source,
hydrogen
donor,
reducing
agent.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(23)
Published: April 20, 2024
Abstract
A
tandem
carbonyl
reduction
and
hydrodefluorination
of
β‐trifluoromethyl
enones
with
hydrosilanes
under
transition‐metal‐free
conditions
was
developed
for
the
synthesis
a
variety
valuable
gem
‐difluorovinyl
alcohols.
The
hydrosilane
could
act
as
both
reductive
agent
C(sp
3
)‐F
bond‐breaking
promoter
mild
reaction
conditions.
Synthetically
useful
organofluorides,
such
‐fluorophosphine
alkene,
ketone,
fluorinated
dihydrofuran
derivatives
be
readily
constructed
by
further
transformations
obtained
Moreover,
method
features
conditions,
operational
simplicity,
excellent
functional
group
tolerance,
scalability.
