Organic Letters,
Год журнала:
2024,
Номер
26(29), С. 6295 - 6300
Опубликована: Июль 15, 2024
The
Rh(II)-catalyzed
enantioselective
S-alkylation
of
sulfenamides
with
α-amide
diazoacetates
at
1
mol
%
catalyst
loading
to
obtain
sulfilimines
in
high
yields
and
enantiomeric
ratios
up
99:1
is
reported.
enantioenriched
sulfilimine
products
incorporate
versatile
amide
functionality
poised
for
further
elaboration
diverse
sulfoximines
multiple
stereogenic
centers,
including
by
highly
diastereoselective
sulfoximine
α-alkylation
alkylating
agents
epoxides
interconversion
the
N-tert-butanesulfinyl
aldimines,
followed
additions.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(39), С. 17808 - 17814
Опубликована: Сен. 26, 2022
Sulfoximines
are
increasingly
incorporated
in
agrochemicals
and
pharmaceuticals,
with
the
two
enantiomers
of
chiral
sulfoximines
often
having
profoundly
different
binding
interactions
biomolecules.
Therefore,
their
application
to
drug
discovery
development
requires
challenging
preparation
single
rather
than
racemic
mixtures.
Here,
we
report
a
general
fundamentally
new
asymmetric
synthesis
sulfoximines.
The
first
S-alkylation
sulfenamides,
which
readily
accessible
sulfur
compounds
one
carbon
nitrogen
substituent,
represents
key
step.
A
broad
scope
for
was
achieved
by
rhodium-catalyzed
coupling
diazo
under
mild
conditions.
When
rhodium
catalyst
utilized
loadings
as
low
0.1
mol
%,
products
were
obtained
high
yields
enantiomeric
ratios
up
98:2
at
newly
generated
center.
efficiently
converted
variety
complete
retention
stereochemistry.
utility
this
approach
further
demonstrated
complex
sulfoximine
agrochemical.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(9), С. 5439 - 5446
Опубликована: Фев. 22, 2023
Direct
construction
of
chiral
S(VI)
from
prochiral
S(II)
is
a
formidable
challenge
due
to
the
inevitable
formation
stable
S(IV).
Previous
synthetic
strategies
rely
on
conversion
S(IV)
or
enantioselective
desymmetrization
preformed
symmetrical
substrates.
Here,
we
report
desymmetrizing
hydrolysis
in
situ-generated
symmetric
aza-dichlorosulfonium
sulfenamides
for
preparation
sulfonimidoyl
chlorides,
which
could
be
used
as
general
synthon
obtaining
series
derivatives.
JACS Au,
Год журнала:
2023,
Номер
3(3), С. 700 - 714
Опубликована: Фев. 28, 2023
Sulfur
can
form
diverse
S(IV)
and
S(VI)
stereogenic
centers,
of
which
some
have
gained
significant
attention
recently
due
to
their
increasing
use
as
pharmacophores
in
drug
discovery
programs.
The
preparation
these
sulfur
centers
enantiopure
has
been
challenging,
progress
made
will
be
discussed
this
Perspective.
This
Perspective
summarizes
different
strategies,
with
selected
works,
for
asymmetric
synthesis
moieties,
including
diastereoselective
transformations
using
chiral
auxiliaries,
enantiospecific
compounds,
catalytic
enantioselective
synthesis.
We
discuss
the
advantages
limitations
strategies
provide
our
views
on
how
field
develop.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(22), С. 15446 - 15452
Опубликована: Май 22, 2024
Linker
installation
is
a
potent
strategy
for
integrating
specific
properties
and
functionalities
into
metal–organic
frameworks
(MOFs).
This
method
enhances
the
structural
diversity
of
enables
precise
construction
robust
structures,
complementing
conventional
postsynthetic
modification
approaches,
by
fully
leveraging
open
metal
sites
active
organic
linkers
at
targeting
locations.
Herein,
we
demonstrated
an
insertion
d-camphorate
linker
flexible
Zr-based
MOF,
PCN-700,
through
installation.
The
resultant
homochiral
MOF
not
only
exhibits
remarkable
stability
but
also
functions
as
highly
efficient
luminescent
material
enantioselective
sensing.
Competitive
absorption
energy/electron
transfer
processes
contribute
to
sensing
performance,
while
difference
in
binding
affinities
dominates
enantioselectivity.
work
presents
straightforward
route
crafting
stable
MOFs
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.
