The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 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.
Synthesis,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 26, 2024
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
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(33), P. 6133 - 6138
Published: Aug. 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.
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
25(22), P. 9092 - 9096
Published: Jan. 1, 2023
An
efficient
iron-catalyzed
sulfur
alkylation
of
sulfenamides
with
diazo
compounds
for
the
synthesis
functionalized
sulfilimines
is
developed
under
air
conditions.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(3)
Published: Nov. 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 Letters,
Journal Year:
2024,
Volume and Issue:
26(18), P. 3816 - 3821
Published: April 30, 2024
A
new
method
to
synthesize
o-bromobenzenethiol
equivalents
through
aryne
intermediates
is
disclosed.
Various
are
prepared
by
the
bromothiolation
of
with
potassium
xanthates.
Aryl
xanthates
serve
in
synthesis
diverse
organosulfurs
involving
phenothiazines
and
thianthrenes
further
transformations.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 27, 2025
The
functionalization
of
N-acylsulfenamides
is
a
research
focus
in
organosulfur
chemistry,
as
the
N-S
array
has
unique
properties
and
versatile
applications.
Although
great
progress
been
made
S-functionalization,
N-functionalization,
especially
N-arylation
N-acylsulfenamides,
rarely
explored
because
lower
nucleophilicity
N-site.
Herein,
we
report
Brønsted
acid-catalyzed
regioselective
reaction
with
o-quinone
diimides.
Under
mild
metal-free
conditions,
wide
range
N-arylated
have
prepared
good
yields
excellent
regioselectivity.
ease
gram-scale
synthesis
transformations
into
useful
sulfonamides
demonstrates
their
synthetic
practicality.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 2, 2025
The
site-selective
incorporation
of
sulfilimine
functionalities
into
aromatic
compounds
provides
a
vital
strategy
for
drug
discovery
in
medicinal
chemistry.
However,
green
and
sustainable
methods
realizing
the
goal
are
still
limited.
Here,
we
report
copper-catalyzed
S-arylation
sulfenamides
with
aryl
thianthrenium
salts
irradiated
by
visible
light
without
photocatalyst,
which
exhibited
fine
functional-group
compatibility
gave
desired
products
high
yields.
Mechanistic
investigations
revealed
that
key
to
achieving
these
results
is
generation
an
electron
donor-acceptor
(EDA)
complex
between
under
basic
conditions.
Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(13), P. 3041 - 3045
Published: May 11, 2024
Abstract
An
efficient
three‐component
reaction
of
biaryl
ynones,
sodium
metabisulfite
and
aryldiazonium
tetrafluoroborates
is
developed.
The
occurs
at
room
temperature
without
any
additives,
thus
offering
a
sustainable
approach
to
access
sulfonyl‐containing
spiro[5,5]trienones.
This
protocol
features
mild
conditions,
broad
substrate
scope
high
functional
group
compatibility,
furnishing
the
target
products
in
moderate
good
yields.
Mechanistic
studies
indicate
that
undergoes
6‐
exo
‐
trig
dearomative
spirocyclization
process
which
initated
by
an
aryl
radical
with
insertion
sulfur
dioxide.
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
general
for
synthesis
N-sulfonyl
sulfilimines
enabled
by
visible-light-mediated
energy
sulfonyl
azides,
uncovering
neglected
reactivity
triplet
nitrenes
sulfides.
The
unprecedented
mechanism
involving
single
electron
broad
group
tolerance,
water
compatibility,
amenability
use
late-stage
functionalization
drugs.
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
general
for
synthesis
N-sulfonyl
sulfilimines
enabled
by
visible-light-mediated
energy
sulfonyl
azides,
uncovering
neglected
reactivity
triplet
nitrenes
sulfides.
The
unprecedented
mechanism
involving
single
electron
broad
group
tolerance,
water
compatibility,
amenability
use
late-stage
functionalization
drugs.
