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.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(48)
Опубликована: Июнь 24, 2024
Abstract
Sulfilimines
and
their
derivatives
have
garnered
considerable
interest
in
both
synthetic
medicinal
chemistry.
Photochemical
nitrene
transfer
to
sulfides
is
known
as
a
conventional
approach
sulfilimines.
However,
the
existing
methods
limited
substrate
scope
stemming
from
incompatibility
of
singlet
intermediates
with
nucleophilic
functional
groups.
Herein,
we
report
synthesis
N
‐sulfonyl
sulfilimines
via
visible‐light‐mediated
energy
sulfonyl
azides,
uncovering
previously
overlooked
reactivity
triplet
nitrenes
sulfides.
This
reaction
features
broad
group
tolerance,
water
compatibility,
amenability
late‐stage
functionalization
drugs.
Thus,
this
work
represents
an
important
example
chemistry
that
overcomes
challenges
traditional
methods.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 16, 2024
In
this
study,
a
metal-free
and
efficient
method
for
the
synthesis
of
sulfilimines
o-sulfanylanilines
in
high
yields
with
excellent
chemoselectivities
from
oxonium
aryne
precursors
sulfenamides
has
been
developed.
This
features
mild
reaction
conditions,
simple
operations,
general
substrate
scope,
good
tolerance
functional
groups.
addition,
scale-up
synthesis,
related
applications,
preliminary
mechanistic
explorations
were
also
investigated.
Organic Letters,
Год журнала:
2023,
Номер
25(49), С. 8861 - 8865
Опубликована: Дек. 7, 2023
Sulfondiimines,
which
are
isoelectronic
with
sulfones
and
sulfoximines,
represent
a
neglected
yet
intriguing
pharmacophore
in
the
discovery
program.
Herein,
we
present
facile
mild
photocatalytic
anti-Markovnikov
hydroamination
of
styrenes
for
construction
N-alkylated
sulfondiimines
primary,
secondary,
tertiary
alkyl
substituents.
A
sulfondiimine-derived
analogue
marketed
drug
Vioxx
was
synthesized
using
this
method
as
key
step.
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.
