The
C–S
bond
is
of
significant
importance
due
to
its
unique
properties
and
diverse
roles
in
chemistry,
biology,
materials
science.
In
this
work,
we
present
an
efficient
synthetic
protocol
a
rapidly
dehydrative
coupling
reaction
with
alcohols
thiols
water
catalyzed
by
triaryl-carbenium
ion
pair.
Under
metal-free
conditions,
wide
range
thioethers
were
obtained
good
yields
(up
99%)
excellent
functional
group
tolerance,
including
the
fast
modification
amino
acid
derivatives
molecules.
This
method
allowed
reactions
be
conducted
low
catalyst
loading,
down
1.0
mol
%,
was
practical
for
gram-scale
synthesis.
Furthermore,
performed
under
biocompatible
making
approach
highly
suitable
potential
bioconjugation.
Organic Letters,
Год журнала:
2024,
Номер
26(12), С. 2500 - 2504
Опубликована: Март 18, 2024
We
developed
a
rhodium-catalyzed
chain-walking
hydrothiolation
process
for
internal
alkenes,
which
offers
novel
and
efficient
alternative
C(sp3)–H
bond
cleavage,
while
focusing
on
thiol
incorporation.
This
method
exclusively
affords
N,S-acetals
at
36–90%
yields.
Regioconvergent
significantly
improved
the
effectiveness
of
this
transformation.
Preliminary
mechanistic
investigations
revealed
that
an
amide-directing
group
is
essential
regioselective
synthesis,
underlining
its
significance
in
process.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(26), С. 17629 - 17635
Опубликована: Июнь 23, 2024
The
total
synthesis
and
structural
elucidation
of
the
antimicrobial
sactipeptide
enteropeptin
A
is
reported.
Enteropeptin
contains
a
thioaminoketal
group
with
an
unassigned
stereochemical
configuration
that
embedded
in
highly
unusual
thiomorpholine
ring.
In
this
synthesis,
linear
peptide
containing
dehydroamino
acid
pendant
cysteine
residue
subjected
to
Markovnikov
hydrothiolation
by
dithiophosphoric
catalyst.
This
cyclization
reaction
forms
central
ring
found
enteropeptins.
Both
diastereomers
at
stereocenter
were
prepared,
their
comparison
authentic
standard
allowed
for
unambiguous
assignment
natural
product
be
D
configuration.
inaugural
represents
first
reported
date.
Moreover,
strategy
disclosed
herein
serves
as
general
platform
stereochemically
defined
thiomorpholine-containing
peptides,
which
may
enable
discovery
new
cyclic
antibiotics.
TMSOTf-mediated
5/6-exo-trig
hydroalkoxylation
followed
by
the
(3
+
2)
cycloaddition
cascade
reaction
of
hydroxy
cyclopropenes
with
aldehydes
gave
an
expedient,
stereoselective
synthesis
[5.5]-and
[6.5]-spiroketal
derivatives.
The
developed
protocol
provides
a
new
approach
toward
spiroketals
from
via
transiently
generated
donor–acceptor
cyclopropane
intermediate.
These
spirocyclic
derivatives
could
be
transformed
to
facilitate
access
intricate
polycyclic
heterocycles
metal
halogen
exchange
and
copper-catalyzed
C–O
cross
coupling
reaction.
decarboxylation
diester
diastereoselectively
sets
fourth
chiral
center
spiroketal
product.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 3, 2025
A
hydropersulfide-mediated
hydrothiolation
reaction
of
alkenes
has
been
developed
for
C-S
bond
formation
with
Markovnikov
selectivity.
This
new
approach
is
a
transition-metal-,
additive-,
and
solvent-free
under
mild
conditions.
The
postulated
to
proceed
by
an
ionic
mechanism
the
release
elemental
sulfur
based
on
our
control
experiments
density
functional
theory
calculations.
The
C–S
bond
is
of
significant
importance
due
to
its
unique
properties
and
diverse
roles
in
chemistry,
biology,
materials
science.
In
this
work,
we
present
an
efficient
synthetic
protocol
a
rapidly
dehydrative
coupling
reaction
with
alcohols
thiols
water
catalyzed
by
triaryl-carbenium
ion
pair.
Under
metal-free
conditions,
wide
range
thioethers
were
obtained
good
yields
(up
99%)
excellent
functional
group
tolerance,
including
the
fast
modification
amino
acid
derivatives
molecules.
This
method
allowed
reactions
be
conducted
low
catalyst
loading,
down
1.0
mol
%,
was
practical
for
gram-scale
synthesis.
Furthermore,
performed
under
biocompatible
making
approach
highly
suitable
potential
bioconjugation.
