Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 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.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(26), P. 17587 - 17594
Published: June 24, 2024
Sulfinamides
have
been
widely
used
in
organic
synthesis,
with
research
on
their
preparation
spanning
more
than
a
century.
Despite
advancements
catalytic
methodologies,
creating
sulfur
stereocenters
within
these
molecules
remains
significant
challenge.
In
this
study,
we
present
an
effective
and
versatile
method
for
synthesizing
diverse
range
of
S-chirogenic
sulfinamides
through
asymmetric
aryl
addition
to
sulfinylamines.
By
utilizing
nickel
complex
as
catalyst,
process
exhibits
impressive
enantioselectivity
can
incorporate
various
arylboronic
acids
at
the
position.
The
resulting
synthetic
are
stable
highly
adaptable,
allowing
conversion
variety
sulfur-containing
compounds.
Our
study
also
incorporates
detailed
experimental
computational
studies
elucidate
reaction
mechanism
factors
influencing
enantioselectivity.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(8), P. 1601 - 1606
Published: Feb. 19, 2024
An
enantioselective
difunctionalization
of
activated
alkynes
using
chiral
sulfinamide
reagents
is
developed.
It
an
atom
and
chirality
transfer
process
that
allows
for
the
modular
synthesis
optically
active
α-amino
acid
derivatives
under
mild
conditions.
The
reaction
proceeds
through
acid-catalyzed
[2,3]-sigmatropic
rearrangement
mechanism
with
predictable
stereochemistry
a
broad
scope.
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
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: March 15, 2025
The
study
of
the
stereochemistry
organic
sulfur
compounds
has
been
ongoing
for
over
a
century,
with
S-chirogenic
pharmacophores
playing
an
essential
role
in
drug
discovery
within
bioscience
and
medicinal
chemistry.
Traditionally,
synthesis
sulfinamides
featuring
stereogenic
sulfur(IV)
centers
involves
complex,
multistep
process
that
often
depends
on
chiral
auxiliaries
or
kinetic
resolution.
Here,
we
introduce
effective
versatile
method
synthesizing
diverse
classes
through
selective
aryl
alkenyl
addition
to
sulfinylamines.
This
is
catalysed
by
nickel
cobalt
complex
under
reductive
conditions,
eliminating
need
preformed
organometallic
reagents.
facilitates
incorporation
array
halides
at
position,
enabling
their
integration
into
various
biologically
significant
pharmacophores.
Our
detailed
mechanistic
investigations
density
functional
theory
calculations
provide
insights
reaction
pathway,
particularly
highlighting
enantiocontrol
mode
during
process.
play
authors
report
methodology
asymmetric
sulfinylamines
via
common-Earth-metal
catalysis.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 18, 2025
The
combination
of
CuI
and
4-(dimethylamino)picolinamide
offers
an
effective
catalytic
system
for
the
successful
coupling
(hetero)aryl
halides
(I
Br)
with
sulfinamides
first
time.
A
large
number
functional
groups
heterocycles
were
tolerated
under
conditions,
providing
a
powerful
approach
diverse
synthesis
pharmaceutically
important
sulfoximines.
efficiency
reaction
was
highly
dependent
upon
electronic
nature
substituents
at
amide
part
sulfinamides.
By
using
enantioenriched
as
partners,
proceeds
in
stereospecific
manner
to
afford
sulfoximines
excellent
enantioselectivity.
