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.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(36)
Published: June 10, 2024
Abstract
S(VI)
compounds
with
multiple
N
or
O
substituents
are
often
difficult
to
make
and
several
crucial
routes,
such
as
multimodal
SuFEx
(Sulfur
(VI)
Fluoride
Exchange)
chemistry,
rely
on
the
highly
useful
but
hazardous
SOF
4
gas.
Safety
issues
inaccessibility
of
strongly
hamper
developments
these
organic
compounds.
Here
we
describe
synthesis
applications
2‐methyl
im
idazole‐1‐(
‐
tert
‐octyl)
s
ulfonimidoyl
f
luoride
(ImSF),
a
novel
bench‐stable
analogue
.
ImSF
is
synthesized
gram
scale
via
double
fluorination
t
‐OctNSO.
We
show
can
undergo
substitution
reactions
phenols
amines,
which
lead
sulfurimidates
sulfuramidimidates,
respectively,
intrinsically
chiral
analogous
medicinally
relevant
sulfates
sulfamates
in
an
S=O
moiety
replaced
by
S=NR
unit.
Finally
demonstrate
that
substitutions
occur
enantiospecifically,
providing
first
entry
sulfuramidimidates.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 18, 2024
Abstract
Nature
offers
a
variety
of
structurally
unique,
sulfated
endobiotics
including
glycosaminoglycans,
tyrosine
peptides,
steroids/bile
acids/catecholamines.
Sulfated
molecules
display
large
number
biological
activities
antithrombotic,
antimicrobial,
anticancer,
anti‐inflammatory,
and
others,
which
arise
from
modulation
intracellular
signaling
enhanced
in
vivo
retention
certain
hormones.
These
characteristics
position
very
favorably
as
drug‐like
agents.
However,
few
have
reached
the
clinic.
Major
hurdles
exist
realizing
drugs.
This
state‐of‐the‐art
has
been
transformed
through
recent
works
on
development
sulfate
masking
technologies
for
both
alkyl
(sulfated
carbohydrates,
steroids)
aryl
(sTyr‐bearing
peptides/proteins,
flavonoids)
sulfates.
review
compiles
literature
different
strategies
implemented
types
groups.
Starting
early
efforts
protection
groups
to
design
newer
SuFEx,
trichloroethyl,
gem‐dimethyl‐based
technologies,
this
presents
evolution
application
concepts
highly
diverse,
candidate
drugs
and/or
prodrugs.
Overall,
demasking
are
likely
greatly
enhance
non‐toxic
future.
Synthesis,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 7, 2024
Abstract
This
year
marks
the
10th
anniversary
of
SuFEx
chemistry,
a
field
that
has
witnessed
significant
advancements
over
past
decade.
These
include
efficient
synthetic
strategies
toward
polymerization
via
approach
leading
to
diverse
polymers,
alongside
discovery
new
SuFExable
hubs
and
coupling
conditions.
Non-canonical
reactions,
such
as
deoxyfluorination
on-water
have
also
emerged.
Furthermore,
there
been
substantial
strides
in
radiosynthesis
[18F]
hubs.
review
provides
an
overview
these
developments,
focusing
on
polymerization,
non-canonical
reaction,
radiochemistry
chemistry.
1
Introduction
2
Polymerization
3
Non-Canonical
Reactions
4
Fluorine-18
Radiochemistry
5
Conclusions
Outlook
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(42), P. 9132 - 9137
Published: Oct. 16, 2024
Both
fluorosulfonyl
and
cyano
groups
are
important
structural
motifs
in
bioactive
molecules.
Herein,
we
report
a
new
difunctionalization
reaction
of
alkenes
based
on
radicals,
which
allows
for
the
introduction
into
unactivated
one
step.
This
transformation
is
enabled
by
merging
photoredox
copper
catalysis,
featuring
visible
light
mild
conditions,
good
functional
group
tolerance.
Further
products
via
SuFEx
reactions
also
demonstrated.
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.
