Abstract
The
pentafluorosulfanyl
group
imparts
exceptional
thermal,
chemical,
and
metabolic
stability
to
organic
scaffolds.
Despite
being
first
described
seven
decades
ago,
it
remains
an
under-utilized
motif
in
organofluorine
chemistry,
primarily
due
a
lack
of
efficient
synthetic
routes
that
proceed
under
mild
reaction
conditions.
Nonetheless,
the
renewed
interest
scaffolds
over
last
decade
has
enabled
preparation
important
building
blocks.
Herein,
major
strategies
for
pentafluoro-λ6-sulfanyl-containing
compounds
are
reviewed,
including
synthesis
(pentafluorosulfanyl)arenes
via
oxidative
halogenation
direct
pentafluorosulfanylation
aliphatic
cores,
achieved
mainly
using
chloride
as
reagent.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(16), С. 3481 - 3493
Опубликована: Апрель 25, 2024
Abstract
We
explored
the
ambiphilic
reactivity
of
SF
5
‐alkynes,
and
we
proved
they
can
act
as
both
nucleophiles
electrophiles.
selected
halogenation
reactions
benchmark
developed
highly
selective
stereodivergent
hydrohalogenation
(I,
Br,
Cl,
F)
‐alkynes.
The
stereochemistry
is
finely
controlled
thanks
to
nature
acids
used
(strong
or
soft)
in
presence
halide
source,
while
high
regioselectivity
governed
by
strong
polarization
Mechanistic
studies
supported
DFT
calculations
shed
light
on
two
different
reaction
mechanisms
responsible
excellent
stereocontrol.
This
stereoselectivity
was
quantitatively
rationalized
with
ASM
EDA
methods.
A
few
dihalogenation
are
reported
rationalize
this
cis
‐stereoselectivity.
Relative
configuration
all
‐haloalkenes
unambiguously
determined
X‐ray
diffraction.
Noteworthy,
several
post‐functionalization
such
cross‐couplings,
cyanation
reductions
described
strengthen
synthetic
potential.
Abstract
This
review
article
outlines
the
literature
from
2022
to
2024
covering
developments
in
SF5
chemistry.
Recent
synthetic
methodologies
of
SF5-containing
building
blocks
are
reported.
These
methods
include
synthesis
SF5Cl
and
its
use
pentafluorosulfanylation
reactions
oxidative
fluorination
reactions.
Moreover,
reactivity
SF5-alkynes
as
versatile
platform
access
new
SF5-compounds
is
described.
Finally,
effects
moiety
highlighted
according
application
different
fields,
such
biological/medicinal
chemistry,
catalysis,
material
sciences.
1
Introduction
2
Access
SF5-Containing
Building
Blocks
2.1
By
Means
2.1.1
Generation
2.2
Oxidative
Fluorination
2.3
SF5-Alkynes
2.4
Other
Miscellaneous
Aromatic
Aliphatic
SF5-Compounds
3
Applications
3.1
Medicinal
Biological
Chemistry
3.2
Material
Science
3.3
Catalysis
4
Conclusion
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Ноя. 9, 2024
Fluorinated
or
fluoroalkylated
alcohols
are
common
structural
motifs
in
biologically
active
molecules,
natural
products,
and
pharmaceuticals.
However,
pentafluorosulfanyl
(SF
Herein
for
the
first
time,
we
disclose
a
practical
and
straightforward
approach
to
access
α-SF5
ketones
via
direct
oxypentafluorosulfanylation
of
alkynes
with
SF5Cl
oxygen
under
acidic
conditions
by
one
step.
The
protocol
features
mild
reaction
conditions,
broad
substrate
scope,
good
functional
group
compatibility
can
be
applied
late-state
functionalization
complex
natural
products
pharmaceuticals.
A
radical
mechanism
involving
SF5
addition
triple
bonds
followed
O2
capture
is
proposed.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(21), С. 15941 - 15952
Опубликована: Окт. 24, 2024
We
disclose
herein
an
efficient
and
facile
method
for
the
synthesis
of
SF5-containing
isoquinolinediones
with
all-carbon
quaternary
stereocenter
via
intramolecular
pentafluorosulfanylation
acrylamides
using
SF5Cl
as
a
reagent.
The
protocol
proceeds
under
mild
reaction
conditions
enjoys
broad
substrate
scope,
wide
functional
group
compatibility,
high
atom-
step-economy.
A
radical
mechanism
involving
SF5
cascade
addition/cyclization
is
proposed.
Chemistry - A European Journal,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 15, 2025
The
pentafluorosulfanyl
(SF5-)
group
has
been
the
subject
of
a
surge
interest
in
past
decade,
but
there
is
still
little
practicality
associated
with
its
synthesis
and
installation.
Herein
reported
first
continuous
flow
chloride
(SF5Cl),
most
common
reagent
for
SF5-substituted
compounds.
based
on
inexpensive
easy-to-handle
reagents:
sulfur
powder
(S8),
trichloroisocyanuric
acid
(TCCA)
potassium
fluoride
(KF).
To
this
end,
custom-made
stirring
reactor
was
designed
to
allow
fast,
safe,
highly
efficient
on-demand
SF5Cl.
resulting
SF5Cl
solution
showcased
radical
addition
alkynes
telescoped
fashion.
The
SF5O
group
has
been
less
explored
as
a
highly
fluorinated
substituent
on
an
organic
framework.
In
fact,
only
few
SF5O-containing
compounds
have
reported,
and
the
preparation
of
relied
hazardous
reagents
special
apparatuses.
Herein
we
describe
safe
efficient
access
to
various
pentafluoro(aryloxy)-λ6-sulfanes
(ArOSF5)
through
reaction
hypervalent
λ3-chlor(brom)anes
with
[Et3MeN]+[OSF5]−.
synthetic
application
potentials
ArOSF5
moieties
were
demonstrated
by
inertness
OSF5
in
presence
palladium
catalysts,
alkalis,
nucleophiles.
Comptes Rendus Chimie,
Год журнала:
2024,
Номер
27(G1), С. 227 - 240
Опубликована: Ноя. 7, 2024
In
the
dynamic
field
of
pentafluorosulfanyl
(SF5)
chemistry,
SF5-alkynes
have
emerged
as
essential,
readily
accessible,
and
modular
building
blocks
for
construction
a
wide
variety
SF5-containing
molecules.
This
polarized
platform
has
been
used
to
perform
highly
regio-,
chemo-,
stereoselective
transformations
such
heterocycle
synthesis,
cycloaddition,
hydroelementation
reactions.
brief
review
provides
an
overview
recent
developments
in
synthesis
reactivity
SF5-alkynes,
which
are
fascinating
that
yet
reveal
their
full
synthetic
potential.
Dans
le
domaine
dynamique
de
la
chimie
du
groupement
pentafluorosulfanyle
(SF5),
les
alcynes
SF5
sont
apparus
comme
des
éléments
base
essentiels,
facilement
accessibles
et
modulaires
pour
d'une
grande
variété
molécules
contenant
SF5.
Cette
plateforme
polarisée
été
utilisée
effectuer
hautement
régio-,
chimio-
stéréosélectives
telles
que
synthèse
d'hétérocycles,
réactions
cycloaddition
d'hydroélémentation.
brève
revue
présente
un
aperçu
dernières
avancées
concernant
réactivité
SF5,
briques
élémentaires
qui
n'ont
pas
encore
révélé
tout
leur
potentiel
synthèse.
