Sulfinate-Promoted Defluorinative Cyclization of Polyfluoroalkyl Tetralones Enabled by Photocatalysis
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 3, 2025
A
Ru-catalyzed
defluorinative
cyclization
of
polyfluoroalkyl
tetralones
has
been
developed
under
visible-light
irradiation
for
the
precise
assembly
γ-pyrones
featuring
α-perfluoroalkyl
and
β-fluorine
substituents.
Selective
functionalization
five
C(sp3)–F
bonds
at
three
carbon
sites
on
perfluoroalkyl
chain
provides
a
new
mode
utilizing
polyfluorides
as
versatile
synthons
to
access
difficult-to-obtain
heterocyclic
scaffolds.
Moreover,
sulfinate
salt
serves
dual
roles
an
oxygen
source
creating
carbonyl
group
defluorinating
promoter.
Язык: Английский
[4+2] Defluorocycloaddition of Perfluoroalkyl Alkynes and Benzylamines: Synthesis of meta-Fluoroalkylated Pyridin-4-amines
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 28, 2025
Pyridines
represent
privileged
heterocycles,
and
the
ability
to
produce
fluorinated
pyridines
from
polyfluorinated
substances
through
selective
defluorofunctionalization
is
a
new
addition
their
synthesis.
Herein,
an
unprecedented
formal
[4+2]
defluorocycloaddition
of
perfluoroalkyl
alkynes
benzylamines
under
metal-free
conditions
described.
By
leveraging
functionalization
four
C(sp3)–F
bonds
on
two
vicinal
sterically
hindered
carbons
alkynes,
diverse
array
meta-fluoroalkylated
pyridin-4-amines
were
synthesized
with
good
functional
group
tolerance.
The
mechanistic
studies
revealed
sequence
hydroamination,
successive
defluorination,
6π-electrocyclization,
aromatization,
amination.
Язык: Английский
Water-Involved 1,3-Aminoxylation of Fluoroalkenes: Chemo-, Regio-, and Stereoselective Synthesis of β-Fluoroacyl Vinylamines
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 9, 2025
Perfluoroalkyl
alkenyl
iodides
(PFAIs)
are
emerging
as
highly
reactive,
storage-stable,
and
multifunctional
fluoroalkyl-bearing
reagents,
facilitating
the
manufacture
of
value-added
organofluorides
through
multi-halo-functionalization.
Herein,
we
developed
a
water-involved
1,3-aminoxylation
PFAIs
with
sulfonamides
for
chemo-,
regio-,
Z-stereoselective
synthesis
valuable
β-fluoroacyl
vinylamines.
This
reaction
proceeded
via
sequential
deiodoamination
defluoroxylation
process
under
transition-metal-free
conditions,
featuring
broad
substrate
scope
good
functional
group
tolerance.
Compared
to
reported
methods,
some
drawbacks,
such
multistep
manipulation,
harsh
need
expensive
catalysts,
use
toxic/sensitive
could
be
eliminated.
Furthermore,
synthetic
potential
this
method
was
demonstrated
scale-up
synthesis,
postfunctionalization
complex
molecules,
ready
transformation
products.
Язык: Английский
Synthesis of trans‐2‐(Disubstituted‐amino)alkenyl Polyoxyperfluoroalkyl Ketones from Tertiary Amines and Perfluoroalkyl Ether Carboxylates Featuring “–CF2O–” Units†
Chinese Journal of Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 25, 2025
Comprehensive
Summary
A
one‐pot
transformation
of
aliphatic
and
aromatic
tertiary
amines
to
novel
fluorinated
enaminones
has
been
developed,
utilizing
perfluoroalkyl
ether
carboxylates
(PFECA
salts)
featuring
“–CF
2
O–”
units
as
the
fluorine‐containing
reagents.
Carbonyl
fluoride,
acyl
fluorides
anhydrides
by
thermal
decomposition
these
PFECA
salts
were
proposed
act
key
active
species
that
trigger
tandem
oxidation–acylation
process
amines,
through
enamine
intermediates.
Язык: Английский