Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(13)
Published: Jan. 30, 2024
Abstract
Sulfilimines,
as
potential
aza‐isosteres
of
sulfoxides,
are
valued
building
blocks,
auxiliaries,
ligands,
bioconjugation
handles,
and
precursors
to
versatile
S(VI)
scaffolds
including
sulfoximines
sulfondiimines.
Here,
we
report
a
thioether
imination
methodology
that
exploits
O‐(diphenylphosphinyl)hydroxyl
amine
(DPPH).
Under
mild,
metal‐free,
biomolecule‐compatible
conditions,
DPPH
enables
late‐stage
S‐imination
on
peptides,
natural
products,
clinically
trialled
drug,
shows
both
excellent
chemoselectivity
broad
functional
group
tolerance.
This
methodological
is
extended
an
efficient
high‐yielding
one‐pot
reaction
for
accessing
free
‐NH
with
diverse
substrates
ones
clinical
importance.
In
the
presence
rhodium
catalyst,
sulfoxides
S‐iminated
in
higher
yields
afford
sulfoximines.
was
validated
oxidatively
delicate
amatoxin
give
sulfilimine
sulfoximine
congeners.
Interestingly,
these
new
sulfoximine‐amatoxins
show
cytotoxicity.
method
further
create
sulfoximine‐Fulvestrant
buthionine
analogues.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(11), P. 6310 - 6318
Published: March 9, 2023
Herein,
an
unprecedented
synthetic
route
to
sulfilimines
via
a
copper-catalyzed
Chan–Lam-type
coupling
of
sulfenamides
is
presented.
A
key
success
in
this
novel
transformation
the
chemoselective
S-arylation
S(II)
form
S(IV)
sulfilimines,
overriding
competitive,
and
more
thermodynamically
favored,
C–N
bond
formation
that
does
not
require
change
sulfur
oxidation
state.
Computations
reveal
selectivity
arises
from
selective
transmetallation
event
where
bidentate
sulfenamide
coordination
through
oxygen
atoms
favors
pathway.
The
mild
environmentally
benign
catalytic
conditions
enable
broad
functional
group
compatibility,
allowing
variety
diaryl
or
alkyl
aryl
be
efficiently
prepared.
Chan–Lam
procedure
could
also
tolerate
alkenylboronic
acids
as
partners
afford
alkenyl
class
scaffolds
cannot
directly
synthesized
conventional
imination
strategies.
benzoyl-protecting
groups
conveniently
removed
product,
which,
turn,
readily
transformed
into
several
S(VI)
derivatives.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(12), P. 2134 - 2138
Published: March 20, 2023
Sulfilimines
are
valuable
compounds
both
in
organic
synthesis
and
pharmaceuticals.
Here
we
developed
a
mild
simplified
method
for
preparation
of
sulfilimines
via
selective
S–C
bond
formation
rather
than
traditional
S–N
formation.
The
is
attractive
useful
the
following
reasons:
it
uses
readily
available
alkylation
reagent
such
alkyl
bromide
or
iodide,
water
as
solvent,
easy
to
perform,
convenient
late-stage
diversification
drugs.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(23), P. 4335 - 4339
Published: June 2, 2023
Sulfilimines
are
key
intermediates
to
common
motifs
in
medicines
and
agrochemicals.
Typically,
this
class
of
compounds
prepared
by
imidation
thioethers,
transition-metal-catalyzed
or
base-promoted
sulfur
alkylation
arylation.
Here,
we
report
a
practical
efficient
base-mediated
arylation
reaction
for
the
preparation
sulfilimines.
A
wide
range
N-acyl
N-aryl
sulfenamides
react
with
various
diaryliodonium
salts
smoothly
afford
sulfilimines
high
yields
excellent
chemoselectivities.
Catalysis Science & Technology,
Journal Year:
2024,
Volume and Issue:
14(9), P. 2320 - 2351
Published: Jan. 1, 2024
Chan–Lam
coupling
has
evolved
as
a
shining
star
among
C–heteroatom
reactions
because
of
its
greener
open
flask
chemistry
and
tremendous
possibilities
in
terms
substrate
bank,
catalyst
varieties,
unlocking
nature
friendly
conditions,
etc.
Science Advances,
Journal Year:
2024,
Volume and Issue:
10(37)
Published: Sept. 13, 2024
Sulfilimines
are
versatile
synthetic
intermediates
and
important
moieties
in
bioactive
molecules.
However,
their
applications
drug
discovery
underexplored,
efficient
asymmetric
methods
highly
desirable.
Here,
we
report
a
transition
metal–free
pentanidium-catalyzed
sulfur
alkylation
of
sulfenamides
with
exclusive
chemoselectivity
over
nitrogen
high
enantioselectivity.
The
reaction
conditions
were
mild,
wide
range
enantioenriched
aryl
alkyl
sulfilimines
obtained.
utility
practicability
this
robust
protocol
further
demonstrated
through
gram-scale
reactions
late-stage
functionalization
drugs.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 12, 2024
A
copper-catalyzed
Ullmann-type
cross-coupling
reaction
of
sulfenamides
with
aryl
iodides
is
developed.
The
key
to
success
the
use
a
2-methylnaphthalen-1-amine-derived
amide
ligand,
which
enables
formation
an
S-C
bond
access
functionalized
sulfilimines
in
good
excellent
yields
at
room
temperature.
This
method
has
advantages
mild
conditions,
broad
substrate
scope,
functional
group
compatibility,
and
high
chemoselectivity.
utility
this
protocol
highlighted
through
late-stage
modification
drug-relevant
molecules
sulfilimine
product
derivatization.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 4, 2025
The
ability
to
chemoselectively
modify
either
the
peptide
backbone
or
specific
side
chains
is
critical
advance
fields
of
bioconjugation
and
pharmaceuticals.
Transition-metal
catalysis
has
been
widely
used
in
protein
derivatization
but
mostly
under
homogeneous
conditions.
Herein,
we
present
a
first-in-class
heterogeneous
catalytic
approach
for
site-selective
functionalization
histidine-containing
peptides
with
aryl
alkenyl
moieties
bearing
fluorescent
affinity
tags,
lipids,
conjugation
handles.
This
strategy
employs
copper(II)
hexacyanometallate
catalyze
Chan-Lam
reaction
boronic
acids
at
histidine
imidazole,
thus
providing
novel
results
that
differ
from
those
previously
reported
Cu(OAc)2-mediated
coupling
procedure.
A
correlation
was
established
between
structural
electronic
properties
hexacyanometalate
its
this
oxidative
cross-coupling.
report
expands
toolbox
late-stage
labeling
by
unlocking
reactivity
chain
rather
than
merely
acting
as
directing
group,
boosting
applications
drug
discovery
development.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(39), P. 7192 - 7197
Published: Sept. 21, 2023
Sulfilimines,
the
aza
analogues
of
sulfoxides,
are
increasing
interest
in
medicinal
and
agrochemical
research
programs.
However,
development
efficient
routes
for
their
synthesis
has
remained
relatively
unexplored.
In
this
study,
we
report
a
transition
metal-free,
selective
S-arylation
reaction
between
sulfenamides
arynes,
enabling
facile
preparation
structurally
diverse
sulfilimines
under
mild
redox-neutral
conditions
good
yields.
The
application
value
our
method
was
further
demonstrated
by
scale-up
synthesis,
downstream
derivatization,
robustness
screen.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(49), P. 8872 - 8876
Published: Dec. 4, 2023
An
efficient
photocatalytic
C–N
cross-coupling
of
nitroarenes
with
haloarenes
has
been
developed
using
simple
and
cheap
Ni(acac)2
as
a
cocatalyst.
The
reaction
is
confirmed
stepwise
process:
(1)
metal
free
photoinduced
reduction
into
aniline
derivatives
(2)
photo-
Ni-catalyzed
anilines
haloarenes.
conditions
are
mild,
giving
high-value
diarylamines
good
to
excellent
yields
functional
group
tolerance.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(13)
Published: Jan. 30, 2024
Abstract
Sulfilimines,
as
potential
aza‐isosteres
of
sulfoxides,
are
valued
building
blocks,
auxiliaries,
ligands,
bioconjugation
handles,
and
precursors
to
versatile
S(VI)
scaffolds
including
sulfoximines
sulfondiimines.
Here,
we
report
a
thioether
imination
methodology
that
exploits
O‐(diphenylphosphinyl)hydroxyl
amine
(DPPH).
Under
mild,
metal‐free,
biomolecule‐compatible
conditions,
DPPH
enables
late‐stage
S‐imination
on
peptides,
natural
products,
clinically
trialled
drug,
shows
both
excellent
chemoselectivity
broad
functional
group
tolerance.
This
methodological
is
extended
an
efficient
high‐yielding
one‐pot
reaction
for
accessing
free
‐NH
with
diverse
substrates
ones
clinical
importance.
In
the
presence
rhodium
catalyst,
sulfoxides
S‐iminated
in
higher
yields
afford
sulfoximines.
was
validated
oxidatively
delicate
amatoxin
give
sulfilimine
sulfoximine
congeners.
Interestingly,
these
new
sulfoximine‐amatoxins
show
cytotoxicity.
method
further
create
sulfoximine‐Fulvestrant
buthionine
analogues.
