The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(22), С. 16426 - 16432
Опубликована: Окт. 31, 2024
We
develop
a
rapid
and
mild
protocol
to
access
sulfonimidoyl
fluoride-[S(VI)]
from
sulfenamide-[S(II)]
directly.
The
transformation
occurs
via
the
reaction
of
sulfenamide
with
NCS
(N-chlorosuccinimide),
water,
TBAF
in
acetonitrile.
Water
act
as
source
for
S═O
bond
formation
fluoride,
respectively.
takes
very
short
time
(within
5
min).
drug
molecules,
such
Carbamazepine
Levetiracetam
attached
fluorides
are
also
achieved
following
this
protocol.
Furthermore,
fluoride
is
transformed
into
sulfonimidamide
presence
AlCl3.
To
best
our
knowledge,
it
first
report
detailing
synthesis
directly
S(II)-sulfenamide.
Journal of Medicinal Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 9, 2025
While
sulfoximines
are
nowadays
a
well
established
functional
group
for
medicinal
chemistry,
the
properties
of
sulfilimines
significantly
less
studied,
and
no
sulfilimine
has
progressed
to
clinic
date.
In
this
account,
physicochemical
in
vitro
reported
compared
those
other
more
traditional
groups.
Furthermore,
impact
on
real
drug
scaffolds
is
studied
two
series
sulfilimine-containing
analogs
imatinib
hNE
inhibitors.
We
show
that
can
be
chemically
configurationally
stable
under
physiologically
relevant
conditions
they
basic
highly
polar
thus
often
beneficial
solubility
metabolic
stability,
although
at
cost
reduced
permeability.
conclude
S-cyclopropyl,S-(hetero)aryl
S,S-di(hetero)aryl
so
far
neglected
but
potentially
valuable
S(IV)
based
pharmacophores
deserve
considered
as
part
chemistry
toolbox.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 2, 2025
Asymmetric
catalysis
involving
a
sulfoxide
electrophile
intermediate
presents
an
efficient
methodology
for
accessing
stereogenic-at-sulfur
compounds,
such
as
sulfinate
esters,
sulfinamides,
etc.,
which
have
garnered
increasing
attention
in
modern
pharmaceutical
sciences.
However,
the
aza-analog
of
electrophiles,
asymmetric
issues
about
electrophilic
sulfinimidoyl
species
remain
largely
unexplored
and
represent
significant
challenge
sulfur
stereochemistry.
Herein,
we
exhibit
anionic
stereogenic-at-cobalt(III)
complex-catalyzed
synthesis
chiral
sulfinamides
via
iodide
intermediates.
Mechanistic
investigations
reveal
that
catalytic
cycle
is
initiated
by
oxidative
iodination,
generating
iodides.
These
active
intermediates
subsequently
undergo
enantiospecific
nucleophilic
substitution
with
water,
affording
diverse
array
enantioenriched
sulfinamides.
Notably,
these
promising
antifungal
activities
against
Sclerotinia
sclerotiorum
serve
ideal
platform
molecules
facilitating
stereospecific
transformation
into
various
stereogenic
aza-sulfur
compounds.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(6)
Опубликована: Дек. 21, 2023
Sulfilimines,
the
aza-variants
of
sulfoxides,
are
key
structural
motifs
in
natural
products,
pharmaceuticals,
and
agrochemicals;
sulfilimine
synthesis
is
therefore
important
organic
chemistry.
However,
methods
for
radical
sulfilimination
remain
elusive,
as
a
result,
diversity
currently
available
sulfilimines
limited.
Herein,
we
report
first
protocol
decarboxylative
reactions
between
sulfenamides
N-hydroxyphthalimide
esters
primary,
secondary,
tertiary
alkyl
carboxylic
acids,
which
were
achieved
via
combination
photoredox,
copper,
Brønsted
base
catalysis.
This
novel
provided
wide
variety
sulfilimines,
addition
to
serving
an
efficient
route
S-alkyl/S-aryl
homocysteine
S-(4-methylphenyl)
sulfoximine.
Moreover,
it
could
be
used
late-stage
introduction
group
into
structurally
complex
molecules,
thereby
avoiding
need
preserve
labile
organosulfur
moieties
through
multistep
synthetic
sequences.
A
mechanism
involving
photocatalytic
substrate
transformation
copper-mediated
C(sp
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(12), С. 9043 - 9050
Опубликована: Июнь 6, 2024
A
mild
and
metal-free
approach
has
been
developed
for
1,2-difunctionalization
of
aryne
using
sulfenamides
as
a
nucleophile
halogen
source
(CX4)
an
electrophile
to
synthesize
S-(o-halo)aryl
sulfilimines.
The
late-stage
functionalizations
halide
handles
via
Suzuki–Miyaura
Buchwald–Hartwig
reactions
exhibit
the
synthetic
utilities
products.
chemoselectivity,
regioselectivity,
rapidity,
use
economical
CCl4
are
advantages
this
protocol.
A
copper-catalyzed
Ullmann-type
cross-coupling
reaction
of
sulfenamides
with
aryl
iodides
is
developed.
The
key
to
success
the
use
a
2-methylnaphthalen-1-amine-derived
amide
ligand,
which
enables
formation
an
S-C
bond
access
functionalized
sulfilimines
in
good
excellent
yields
at
room
temperature.
This
method
has
advantages
mild
conditions,
broad
substrate
scope,
functional
group
compatibility,
and
high
chemoselectivity.
utility
this
protocol
highlighted
through
late-stage
modification
drug-relevant
molecules
sulfilimine
product
derivatization.
Organic Letters,
Год журнала:
2023,
Номер
25(39), С. 7192 - 7197
Опубликована: Сен. 21, 2023
Sulfilimines,
the
aza
analogues
of
sulfoxides,
are
increasing
interest
in
medicinal
and
agrochemical
research
programs.
However,
development
efficient
routes
for
their
synthesis
has
remained
relatively
unexplored.
In
this
study,
we
report
a
transition
metal-free,
selective
S-arylation
reaction
between
sulfenamides
arynes,
enabling
facile
preparation
structurally
diverse
sulfilimines
under
mild
redox-neutral
conditions
good
yields.
The
application
value
our
method
was
further
demonstrated
by
scale-up
synthesis,
downstream
derivatization,
robustness
screen.
Organic Letters,
Год журнала:
2023,
Номер
25(33), С. 6133 - 6138
Опубликована: Авг. 14, 2023
In
this
work,
a
facile
and
efficient
method
for
the
synthesis
of
sulfilimines
through
multicomponent
reaction
arynes,
sulfamides,
thiosulfonates
was
developed.
A
variety
structurally
diverse
substrates
functional
groups
were
very
compatible
in
reaction,
giving
corresponding
good
to
high
yields.
This
protocol
could
be
conducted
on
gram
scale,
product
easily
converted
sulfide
sulfoximine.
Mechanism
studies
revealed
that
sulfenamide
generated
situ
is
key
intermediate
reaction.
Organic Letters,
Год журнала:
2024,
Номер
26(18), С. 3906 - 3910
Опубликована: Апрель 29, 2024
Sulfilimines
are
valuable
compounds
in
both
organic
synthesis
and
pharmaceuticals.
In
this
study,
we
present
a
copper-catalyzed
sulfur
alkylation
of
sulfenamides
with
