Angewandte Chemie,
Год журнала:
2023,
Номер
136(3)
Опубликована: Ноя. 28, 2023
Abstract
A
general
one‐pot
approach
to
diverse
N
‐acylsulfenamides
from
a
common
S
‐phenethylsulfenamide
starting
material
is
reported.
This
was
demonstrated
by
C−S
bond
formation
utilizing
commercially
abundant
(hetero)aryl
iodides
and
boronic
acids
provide
sulfilimine
intermediates
that
undergo
thermal
elimination
of
styrene.
In
contrast,
all
prior
approaches
rely
on
thiol
inputs
introduce
sulfenamide
‐substituents.
broad
scope
reaction
including
for
approved
drugs
drug
precursors
with
dense
display
functionality.
Several
different
types
sulfur
functionalization
were
performed
derived
complex
precursor
the
blockbuster
anticoagulant
apixaban,
highlighting
utility
this
introduction
high
oxidation
state
groups
in
bioactive
compounds.
Mechanistic
studies
established
key
styrene
step
proceeds
concerted
does
not
require
reagents
or
catalysts,
therefore,
should
be
applicable
synthesis
electrophiles
conditions
formation.
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.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(23), С. 16116 - 16121
Опубликована: Ноя. 20, 2023
Herein,
we
present
a
copper-catalyzed
oxidative
amination
of
sulfenamides
for
the
synthesis
sulfinamidines.
By
employment
air
as
terminal
oxidant,
diverse
array
secondary
and
primary
amines
can
be
efficiently
transformed
into
their
corresponding
products.
This
method
is
well-suited
last-stage
functionalization,
underlying
mechanism
has
been
investigated.
The
transformation
characterized
by
exceptional
chemoselectivity,
mild
conditions,
facile
operation,
broad
substrate
compatibility,
which
have
significant
implications
fields
pharmaceuticals
organic
synthesis.
Abstract
Sulfur-containing
compounds
are
found
in
myriad
applications.
Sulfones
and
sulfonamides
the
most
common
functional
groups
used
medicinal
agrochemical
endeavours.
Isosteres
of
these
groups,
for
example,
sulfoximines
sulfonimidamides,
emerging
functionalities,
they
increasingly
relevant
patent
literature.
However,
general,
associated
synthetic
routes
still
have
limitations,
including
use
harsh
reaction
conditions
highly
reactive
reagents.
A
variety
catalytic
reactions
that
employ
a
diverse
range
substrate
classes
been
developed
to
address
issues.
This
short
review
highlights
recent
syntheses
aza-sulfur
compounds,
which
we
hope
will
open
new
directions
discovery
chemistry.
1
Introduction
2
Reactions
N-Sulfinylamines
3
with
Sulfenamides
4
Sulfinates
5
Sulfinamides
6
Other
Aza-Sulfur
Compounds
7
Conclusion
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(3)
Опубликована: Ноя. 28, 2023
Abstract
A
general
one‐pot
approach
to
diverse
N
‐acylsulfenamides
from
a
common
S
‐phenethylsulfenamide
starting
material
is
reported.
This
was
demonstrated
by
C−S
bond
formation
utilizing
commercially
abundant
(hetero)aryl
iodides
and
boronic
acids
provide
sulfilimine
intermediates
that
undergo
thermal
elimination
of
styrene.
In
contrast,
all
prior
approaches
rely
on
thiol
inputs
introduce
sulfenamide
‐substituents.
broad
scope
reaction
including
for
approved
drugs
drug
precursors
with
dense
display
functionality.
Several
different
types
sulfur
functionalization
were
performed
derived
complex
precursor
the
blockbuster
anticoagulant
apixaban,
highlighting
utility
this
introduction
high
oxidation
state
groups
in
bioactive
compounds.
Mechanistic
studies
established
key
styrene
step
proceeds
concerted
does
not
require
reagents
or
catalysts,
therefore,
should
be
applicable
synthesis
electrophiles
conditions
formation.
Organic & Biomolecular Chemistry,
Год журнала:
2023,
Номер
21(38), С. 7681 - 7690
Опубликована: Янв. 1, 2023
Significant
advancements
have
recently
been
made
in
the
chemistry
of
sulfinamidines
and
sulfinimidate
esters.
This
review
aims
to
provide
an
overview
synthetic
methods
for
preparation
transformation
these
overlooked
compounds.
ACS Sustainable Chemistry & Engineering,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 15, 2025
Herein,
we
present
a
metal-/catalyst-free,
novel
approach
for
S-sulfoximination
of
sulfenamide.
The
electrooxidative
reactions
sulfenamides
and
sulfoximines
are
fast,
high-yielding,
atom-economical
(99.5%),
broad-substrate-tolerant,
free
from
supporting
electrolytes.
protocol
is
ecofriendly
shows
wider
substrate
tolerance
than
previous
reports.
drug-attached
sulfenamide
(levetiracetam)
sulfoximine
(albendazole)
also
undergo
the
reaction
efficiently.
A
possible
mechanistic
pathway
proposed.
Fascinatingly,
target
products
obtained
via
photochemical
in
presence
photocatalyst
eosin
Y.
Organic & Biomolecular Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
In
this
work,
we
present
an
innovative
Brønsted
acid-catalyzed
approach
for
the
concurrent
preparation
of
sulfinamidines
and
sulfinimidate
esters
from
sulfenamides
under
one
set
mild
metal-free
conditions,
employing
electrophilic
fluorination
followed
by
nucleophilic
substitution,
achieving
high
yields
up
to
97%
after
12
hours
at
room
temperature.
This
reaction
method
is
enabled
CSA
as
acid
catalyst,
Selectfluor
fluorinating
reagent,
readily
available
amines
alcohols
nucleophiles.
The
proposed
mechanism
involves
initial
sulfur
atom,
attack.
protocol
easily
scalable
compatible
with
various
substrates.
Our
allows
gram-scale
preparation,
these
S(IV)
products
can
be
further
oxidized
S(VI)
derivatives,
expanding
their
potential
applications
in
medicinal
chemistry
beyond.
Importantly,
shows
considerable
late-stage
functionalization
drugs,
demonstrating
its
promise
new
drug
discovery
development.
