Angewandte Chemie,
Год журнала:
2023,
Номер
135(21)
Опубликована: Март 18, 2023
Abstract
Metal‐polarized
aza‐
ortho
‐quinone
methides
(aza‐
o
‐QMs)
are
a
unique
and
efficient
handle
for
azaheterocycle
synthesis.
Despite
great
achievements,
the
potential
of
these
reactive
intermediates
has
not
yet
been
fully
exploited,
especially
new
reaction
modes.
Herein,
we
disclosed
an
unprecedented
dearomatization
process
metal‐polarized
‐QMs,
affording
transient
dearomatized
spiroaziridine
intermediates.
Based
on
this
serendipity,
accomplished
three
sequential
dearomatization‐rearomatization
reactions
benzimidazolines
with
aza‐sulfur
ylides,
enabling
divergent
synthesis
bis‐nitrogen
heterocycles
high
efficiency
flexibility.
Moreover,
experimental
theoretical
studies
were
performed
to
explain
proposed
mechanisms
observed
selectivity.
Further
cellular
evaluation
dibenzodiazepine
products
identified
hit
compound
antitumor
drugs.
Organic Letters,
Год журнала:
2023,
Номер
25(12), С. 2134 - 2138
Опубликована: Март 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.
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,
Год журнала:
2022,
Номер
144(27), С. 12476 - 12487
Опубликована: Июнь 29, 2022
Inspired
by
the
discovery
of
a
S═N
bond
in
collagen
IV
network
and
its
essential
role
stabilizing
basement
membranes,
sulfilimines
have
drawn
much
attention
fields
chemistry
biology.
However,
their
further
uptake
is
hindered
lack
mild,
efficient,
environmentally
benign
protocols
which
can
be
constructed
under
biomolecule-compatible
conditions.
Here,
we
report
terminal
oxidant-free
copper-catalyzed
dehydrogenative
Chan–Lam
coupling
free
diaryl
with
arylboronic
acids
excellent
chemoselectivity
broad
substrate
compatibility.
The
mild
reaction
conditions
nature
allow
employment
this
protocol
late-stage
functionalization
complex
peptides,
more
importantly,
as
an
effective
bioconjugation
method
showcased
model
protein.
A
combined
experimental
computational
mechanistic
investigation
reveals
that
inner-sphere
electron-transfer
process
circumvents
sacrificial
oxidant
employed
traditional
reactions.
An
energetically
viable
concerted
pathway
was
located
wherein
copper
hydride
facilitates
hydrogen-atom
abstraction
from
isopropanol
solvent
to
produce
dihydrogen
via
four-membered
transition
state.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(21)
Опубликована: Март 18, 2023
Metal-polarized
aza-ortho-quinone
methides
(aza-o-QMs)
are
a
unique
and
efficient
handle
for
azaheterocycle
synthesis.
Despite
great
achievements,
the
potential
of
these
reactive
intermediates
has
not
yet
been
fully
exploited,
especially
new
reaction
modes.
Herein,
we
disclosed
an
unprecedented
dearomatization
process
metal-polarized
aza-o-QMs,
affording
transient
dearomatized
spiroaziridine
intermediates.
Based
on
this
serendipity,
accomplished
three
sequential
dearomatization-rearomatization
reactions
benzimidazolines
with
aza-sulfur
ylides,
enabling
divergent
synthesis
bis-nitrogen
heterocycles
high
efficiency
flexibility.
Moreover,
experimental
theoretical
studies
were
performed
to
explain
proposed
mechanisms
observed
selectivity.
Further
cellular
evaluation
dibenzodiazepine
products
identified
hit
compound
antitumor
drugs.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(13)
Опубликована: Янв. 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.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
88(20), С. 14587 - 14600
Опубликована: Окт. 11, 2023
A
Yb(OTf)3-catalyzed
formal
(4
+
3)
cycloaddition
reaction
of
donor-acceptor
cyclopropanes
with
3-benzylideneindoline-2-thiones
as
sulfur-containing
4π
components
has
been
successfully
achieved.
series
functionalized
5,10-dihydro-2H-thiepino[2,3-b]indole
derivatives
were
synthesized
good
yields
and
moderate
to
diastereoselectivity.
The
described
herein
represented
the
inaugural
3-benzylideneindoline-2-thiones.
Chemical Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Янв. 1, 2024
A
method
of
introducing
sulfilimines
fragment
such
as
drugs,
natural
products,
bioactive
handles,
and
fluorescent
tags
into
peptides
at
their
acid
sites
was
disclosed
via
an
intermolecular
sulfur
atom
transfer
cascade
reaction,
both
in
the
homogeneous
phase
and/or
on-resins
SPPS.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(9), С. 2294 - 2300
Опубликована: Янв. 1, 2023
An
efficient
one-pot,
two-step,
three-component
reaction
of
isatin-derived
MBH
carbonates,
sulfilimines,
and
epoxides
was
achieved,
thus
affording
pharmaceutically
important
spiro-oxindole
dihydropyridines.
Organic Letters,
Год журнала:
2022,
Номер
24(6), С. 1362 - 1366
Опубликована: Фев. 4, 2022
Developing
efficient
strategies
for
synthesizing
novel
diazocine
compounds
is
valuable
because
their
use
has
been
limited
by
synthetic
accessibility.
This
work
describes
the
catalytic
(4+3)
cycloaddition
reaction
of
carbonyl
ylides
with
azoalkenes
generated
in
situ.
The
rhodium-catalyzed
cascade
features
good
atom
and
step
economy,
providing
first
access
to
oxo-bridged
diazocines.
product
could
be
synthesized
on
a
gram
scale
converted
into
diversely
substituted
dihydroisobenzofurans.
