Angewandte Chemie,
Год журнала:
2024,
Номер
unknown
Опубликована: Ноя. 5, 2024
Abstract
Sulfur‐centered
electrophilic
‘warheads’
have
emerged
as
key
components
for
chemical
proteomic
probes
through
sulfur‐exchange
chemistry
(SuFEx)
with
protein
nucleophiles.
Among
these
functional
groups,
sulfonimidoyl
fluorides
(SIFs)
stand
out
their
modifiable
sites,
tunable
electrophilicities,
and
chiral
sulfur‐center,
presenting
exciting
possibilities
new
covalent
probes.
However,
the
synthetic
access
to
SIFs
has
been
a
challenge,
limiting
exploration
applications.
In
this
study,
we
describe
convenient
route
obtain
from
readily
available
sulfenamides
via
series
of
one‐pot
tandem
reactions
high
enantiomeric
excess
(ees).
The
resulting
were
further
converted
into
diverse
array
S(VI)
derivatives
under
mild
conditions
or
in
buffer
solutions.
Most
significantly,
specificity
ligation
experiments
underscored
critical
role
sulfur‐center
chirality
design
screening
more‐selective
therapeutics.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Янв. 25, 2024
Abstract
Sulfur(VI)
fluoride
exchange,
a
new
type
of
linkage
reaction,
has
excellent
potential
for
application
in
functional
molecule
to
prepare
pharmaceuticals,
biomolecules,
and
polymers.
Herein,
C-SuFEx
reaction
is
established
achieve
fast
(in
minutes)
between
sulfonimidoyl
fluorides
aryl/alkyl
organotrifluoroborates.
Potassium
organotrifluoroborates
are
instantaneously
activated
via
substoichiometric
amount
trimethylsilyl
triflate
afford
organodifluoroboranes,
releasing
BF
3
as
an
activating
reagent
situ.
This
sulfur(VI)
exchange
technique
capable
forming
S(VI)-C(alkyl),
S(VI)-C(alkenyl)
S(VI)-C(aryl)
bonds,
demonstrating
its
broad
scope.
Natural
products
pharmaceuticals
with
sensitive
groups,
such
valdecoxib,
celecoxib
diacetonefructose,
compatible
this
protocol,
allowing
the
formation
diverse
sulfoximines.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Авг. 24, 2023
Sulfonyl
and
sulfonimidoyl
fluorides
are
versatile
substrates
in
organic
synthesis
medicinal
chemistry.
However,
they
have
been
exclusively
used
as
S(VI)+
electrophiles
for
defluorinative
ligations.
Converting
sulfonyl
to
S(VI)
radicals
is
challenging
underexplored
due
the
strong
bond
dissociation
energy
of
SVI-F
high
reduction
potentials,
but
once
achieved
would
enable
dramatically
expanded
synthetic
utility
downstream
applications.
In
this
report,
we
disclose
a
general
platform
address
issue
through
cooperative
organosuperbase
activation
photoredox
catalysis.
Vinyl
sulfones
sulfoximines
obtained
with
excellent
E
selectivity
under
mild
conditions
by
coupling
reactions
alkenes.
The
method
preparation
functional
polymers
dyes
also
demonstrated.
Chemical Science,
Год журнала:
2023,
Номер
14(46), С. 13384 - 13391
Опубликована: Янв. 1, 2023
Sulfinamides
are
some
of
the
most
centrally
important
four-valent
sulfur
compounds
that
serve
as
critical
entry
points
to
an
array
emergent
medicinal
functional
groups,
molecular
tools
for
bioconjugation,
and
synthetic
intermediates
including
sulfoximines,
sulfonimidamides,
sulfonimidoyl
halides,
well
a
wide
range
other
S(iv)
S(vi)
functionalities.
Yet,
accessible
chemical
space
sulfinamides
remains
limited,
approaches
largely
confined
two-electron
nucleophilic
substitution
reactions.
We
report
herein
direct
radical-mediated
decarboxylative
sulfinamidation
first
time
enables
access
from
broad
structurally
diverse
carboxylic
acids.
Our
studies
show
formation
prevails
despite
inherent
thermodynamic
preference
radical
addition
nitrogen
atom,
while
machine
learning-derived
model
facilitates
prediction
reaction
efficiency
based
on
computationally
generated
descriptors
underlying
reactivity.
Organic Letters,
Год журнала:
2023,
Номер
25(48), С. 8722 - 8726
Опубликована: Ноя. 29, 2023
A
photochemical
halogen-atom
transfer
(XAT)
method
for
generating
sulfonyl
radicals
from
aryl
fluorides
has
been
developed.
It
allows
the
hydrosulfonylation
of
unactivated
alkenes,
which
was
challenging
to
achieve
through
our
previous
single-electron
route.
This
reaction
excellent
functional
group
tolerance
and
substrate
scope
under
mild
conditions.
This
study
reported
a
novel
and
unprecedented
photoredox-catalyzed
protocol
for
direct
allylic
C–H
fluorosulfonylation
of
alkenes
with
FABI.
mild
exhibited
excellent
compatibility
various
functional
groups,
broad
substrate
scope,
promising
scalability,
enabling
convenient
access
to
wide
range
allyl
sulfonyl
fluorides
exceptional
regioselectivity.
The
synthetic
robustness
this
strategy
was
further
demonstrated
by
the
late-stage
functionalization
natural
products
their
ligation
other
drugs
via
SuFEx
chemistry.
Organic & Biomolecular Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
An
N-heterocyclic
carbene
(NHC)-catalyzed
SuFEx
reaction
of
fluoroalkylated
secondary
benzylic
alcohols
with
sulfonyl
fluorides
and
fluorosulfates
affords
fluorinated
sulfonates
sulfates
in
high
yields.
Here,
we
report
the
use
of
iminosulfur
oxydifluorides,
derived
from
SOF4
and
primary
amines,
for
generation
unprecedented
aza-analogues
fluorosulfury
azide
(FSO2N3),
namely,
fluorosulfonimidoyl
(R-N═SOFN3).
Unlike
FSO2N3,
R-N═SOFN3
acts
as
a
sulfamoyl
nitrene
precursor,
undergoing
imidation
with
sulfoxides
thioethers
to
products
featuring
unique
"-N
=
S(VI)F-N
S(VI)-"
linkages
without
metal
catalyst.
The
fluoride
at
S(VI)
center
can
be
sequentially
exchanged
generate
diverse
three-deminsional
structures
tunable
SuFEx
reactivity.
Mechanistic
studies
reveal
that
R-N
SOFN3
decomposes
intermediate,
which
is
stabilized
by
adjacent
"-S(VI)=N-"
nitrogen
atom.
This
facilitates
formation
three-membered
rings
react
further
S(IV)/S(II).
These
novel
transformations
expand
scope
SOF4-based
chemistry,
demonstrating
enables
dual
reactivity
through
both
nitrene-driven
SuFEx-based
linkages.
