Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(29), P. 6295 - 6300
Published: July 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.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: July 26, 2024
Abstract
A
general
phase‐transfer
catalyst
(PTC)
mediated
enantioselective
alkylation
of
N
‐acylsulfenamides
is
reported.
Essential
to
achieving
high
selectivity
was
the
use
triethylacetyl
sulfenamide
protecting
group
along
with
aqueous
KOH
as
base
under
biphasic
conditions
enable
reaction
be
performed
at
−40
°C.
With
these
key
parameters,
enantiomeric
ratios
up
97.5
:
2.5
newly
generated
chiral
sulfur
center
were
achieved
an
inexpensive
cinchona
alkaloid
derived
PTC.
Broad
scope
and
excellent
functional
compatibility
observed
for
a
variety
S
‐(hetero)aryl
branched
unbranched
‐alkyl
sulfenamides.
Moreover,
achieve
opposite
enantiomer,
pseudoenantiomeric
designed
synthesized
from
cinchonidine.
Given
that
sulfoximines
are
bioactive
pharmacophore
ever‐increasing
interest,
selected
product
sulfilimines
oxidized
corresponding
subsequent
reductive
cleavage
affording
free‐NH
in
yields.
The
utility
disclosed
method
further
demonstrated
by
efficient
asymmetric
synthesis
atuveciclib,
phase
I
clinical
candidate
which
only
HPLC
separation
had
previously
been
reported
isolation
desired
(
R
)‐sulfoximine
stereoisomer.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(14), P. 5333 - 5339
Published: Jan. 1, 2024
Starting
from
N
,
-dichloramines
and
S
8
or
disulfides,
azasulfur(
iv
)
chlorides
are
prepared,
which
easily
derivatised
by
esterification
amidation.
The
resulting
products
can
be
converted
to
a
variety
of
complex
sulfur(
vi
compounds.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: May 22, 2024
Abstract
The
enantioselective
synthesis
of
S
-stereogenic
sulfinamides
has
garnered
considerable
attention
due
to
their
structural
and
physicochemical
properties.
However,
catalytic
asymmetric
still
remains
daunting
challenges,
impeding
broad
application
in
drug
discovery
development.
Here,
we
present
an
approach
for
the
through
peptide-mimic
phosphonium
salt-catalyzed
skeletal
reorganization
simple
prochiral
and/or
racemic
sulfoximines.
This
methodology
allows
facile
access
a
diverse
array
substituted
with
excellent
enantioselectivities,
accommodating
various
substituent
patterns
desymmetrization
or
parallel
kinetic
resolution
process.
Mechanistic
experiments,
coupled
density
functional
theory
calculations,
clarify
stepwise
pathway
involving
ring-opening
ring-closing
processes,
step
identified
as
crucial
achieving
stereoselective
control.
Given
prevalence
centers
pharmaceuticals,
anticipate
that
this
protocol
will
enhance
efficient
precise
relevant
chiral
molecules
analogs,
thereby
contributing
advancements
discovery.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(29), P. 6295 - 6300
Published: July 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.
