Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(29)
Published: May 19, 2023
Abstract
Sulfur(VI)‐fluoride
exchange
(SuFEx)
chemistry,
an
all‐encompassing
term
for
substitution
events
that
replace
fluoride
at
electrophilic
sulfur(VI),
enables
the
rapid
and
flexible
assembly
of
linkages
around
a
S
VI
core.
Although
myriad
nucleophiles
applications
works
very
well
with
SuFEx
concept,
electrophile
design
has
remained
largely
SO
2
‐based.
Here,
we
introduce
S≡N‐based
fluorosulfur(VI)
reagents
to
realm
chemistry.
Thiazyl
trifluoride
(NSF
3
)
gas
is
shown
serve
as
excellent
parent
compound
hub
efficiently
synthesize
mono‐
disubstituted
fluorothiazynes
in
ex
situ
generation
workflow.
Gaseous
NSF
was
evolved
from
commercial
nearly
quantitative
fashion
ambient
conditions.
Moreover,
mono‐substituted
thiazynes
could
be
extended
further
handles
engaged
synthesis
unsymmetrically
thiazynes.
These
results
provide
valuable
insights
into
versatility
these
understudied
sulfur
functionalities
paving
way
future
applications.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(23)
Published: May 25, 2024
Abstract
Sulfonyl
fluorides
have
widespread
applications
in
many
fields,
including
organic
synthesis,
chemical
biology,
drug
discovery
and
materials
science.
In
particular,
the
past
decade,
a
number
of
aliphatic
sulfonyl
been
identified
showing
various
biological
activities.
These
appealing
features
brought
about
significant
advancement
developing
synthetic
methods
to
access
fluorides.
this
review,
we
will
discuss
recent
developments
radical
approaches
for
synthesis
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(24), P. 4478 - 4482
Published: June 12, 2023
Multicomponent
reactions
represent
a
powerful
method
for
building
complex
molecules
from
structurally
simple
starting
materials.
Herein,
we
report
novel
three-component
radical–polar
crossover
reaction
involving
tandem
addition
of
two
different
olefins,
which
is
initiated
by
the
selective
fluorosulfonyl
radicals
to
alkyl
alkenes.
This
process
provides
facile
and
effective
access
multiple
functionalized
aliphatic
sulfonyl
fluoride
molecules.
Further
transformation
products
also
demonstrated.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(36)
Published: July 12, 2022
Abstract
The
products
of
the
SuFEx
reaction
between
sulfonimidoyl
fluorides
and
phenols,
sulfonimidates,
are
shown
to
display
dynamic
covalent
chemistry
with
other
phenols.
This
was
be
enantiospecific,
finished
in
minutes
at
room
temperature
high
yields,
useful
for
both
asymmetric
synthesis
sustainable
polymer
production.
Its
wide
scope
further
extends
usefulness
related
click
chemistries.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(30), P. 5666 - 5670
Published: July 25, 2023
Reaction
of
sulfonimidoyl
fluorides
with
anilines
and
Ca(NTf2)2
results
in
the
formation
chiral
sulfonimidamides.
The
reaction
proceeds
inversion
stereocenter
at
a
sulfur
atom.
Enantiospecificity
was
observed
for
all
studied
non-heterocyclic
anilines.
Combined
experimental
computational
mechanistic
studies
highlight
chelate-type
coordination
group
to
SN2-like
transition
state,
which
leaving
F–
coordinates
Ca2+
ion.
ACS Polymers Au,
Journal Year:
2023,
Volume and Issue:
3(3), P. 259 - 266
Published: Jan. 17, 2023
Polysulfamides
are
the
-SO2-
analogues
of
polyureas
and
form
an
intriguing
family
polymers
containing
hydrogen-bond
donor
acceptor
groups.
However,
unlike
polyureas,
their
physical
properties
mostly
unknown
because
scarcity
synthetic
methods
to
access
such
polymers.
Herein,
we
report
expedient
synthesis
AB
monomers
for
polysulfamides
via
Sulfur(VI)
Fluoride
Exchange
(SuFEx)
click
polymerization.
Upon
optimization
step-growth
process,
a
variety
were
isolated
characterized.
The
versatility
SuFEx
polymerization
allowed
structural
modulation
main
chain
through
incorporation
aliphatic
or
aromatic
amines.
While
all
synthesized
presented
high
thermal
stability
thermogravimetric
analysis,
glass-transition
temperature
crystallinity
shown
be
highly
tied
structure
backbone
between
repeating
sulfamide
units
differential
scanning
calorimetry
powder
X-ray
diffraction.
Careful
analysis
matrix-assisted
laser
desorption/ionization
time-of-flight
mass
spectrometry
crystallography
also
revealed
formation
macrocyclic
oligomers
during
one
monomer.
Finally,
two
protocols
developed
efficiently
degrade
either
chemical
recycling
derived
from
amines
oxidative
upcycling
those
based
on
Science Advances,
Journal Year:
2024,
Volume and Issue:
10(37)
Published: Sept. 13, 2024
Sulfilimines
are
versatile
synthetic
intermediates
and
important
moieties
in
bioactive
molecules.
However,
their
applications
drug
discovery
underexplored,
efficient
asymmetric
methods
highly
desirable.
Here,
we
report
a
transition
metal–free
pentanidium-catalyzed
sulfur
alkylation
of
sulfenamides
with
exclusive
chemoselectivity
over
nitrogen
high
enantioselectivity.
The
reaction
conditions
were
mild,
wide
range
enantioenriched
aryl
alkyl
sulfilimines
obtained.
utility
practicability
this
robust
protocol
further
demonstrated
through
gram-scale
reactions
late-stage
functionalization
drugs.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(15), P. 3202 - 3207
Published: April 5, 2024
Here,
we
present
the
straightforward
synthesis
of
N-fluorosulfonyl
guanidine
(1)
from
two
industrial
feedstocks,
hydrochloride
and
sulfuryl
fluoride
(SO2F2),
using
SuFEx
chemistry.
Compound
1
exhibits
excellent
stability
under
ambient
conditions
displays
unique
reactivity
toward
amines
phenols
to
generate
N-guanyl
sulfamides
sulfamates
that
have
rarely
been
accessed.
Notably,
water
serves
as
an
effective
solvent
in
this
process.
Our
protocol
provides
a
reliable
pathway
for
investigation
these
novel
guanidine-containing
molecules.
Abstract
Phosphorus
Fluoride
Exchange
(PFEx)
is
a
new
click
chemistry
technology
that
hinges
on
the
creation
of
innovative
hubs
to
unlock
its
potential
and
broaden
applications.
In
this
study,
we
outline
some
guiding
principles
for
PFEx
hub
development
validate
these
by
developing
hub,
2‐substituted‐alkynyl‐1‐cyclotriphosphazenes
(SACPs).
These
SACPs
serve
as
versatile
with
stable
functionality
orthogonal
reactivity,
exemplifying
their
utility
within
Diversity
Oriented
Clicking
(DOC)
framework.
We
demonstrate
interact
various
1,3‐dipoles,
enabling
synthesis
phosphorus‐rich
compounds
through
sequential
cycloaddition
reactions,
thus
pioneering
synthetic
routes
wide
application
chemistry.
