Angewandte Chemie,
Год журнала:
2022,
Номер
135(8)
Опубликована: Дек. 22, 2022
Abstract
Efficient
protocols
for
accessing
iodo‐substituted
diaryl
and
aryl(vinyl)
sulfides
have
been
developed
using
iodonium
salts
as
reactive
electrophilic
arylation
vinylation
reagents.
The
reactions
take
place
under
transition‐metal‐free
conditions,
employing
odorless
convenient
sulfur
A
wide
variety
of
functional
groups
are
tolerated
in
the
S
‐diarylation,
enabling
regioselective
late‐stage
application
several
heterocycles
drug
molecules
mild
reaction
conditions.
novel
‐difunctionalization
pathway
was
discovered
vinyliodonium
salts,
which
proceeds
additive‐free
conditions
grants
excellent
stereoselectivity
synthesis
sulfides.
one‐pot
strategy
combining
diarylation
subsequent
reduction
provided
facile
access
to
electron‐rich
thioanilines
a
direct
potential
candidate
derivative.
retained
iodo
group
allows
array
further
synthetic
transformations.
Mechanistic
insights
were
elucidated
by
isolating
key
intermediate,
relevant
energy
profile
substantiated
DFT
calculations.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(22)
Опубликована: Март 16, 2022
Abstract
The
synthesis
of
sulfides
has
been
widely
studied
because
this
functional
subunit
is
prevalent
in
biomolecules
and
pharmaceuticals,
as
well
being
a
useful
synthetic
platform
for
further
elaboration.
Thus,
various
methods
to
build
C−S
bonds
have
developed,
but
typically
they
require
the
use
precious
metals
or
harsh
conditions.
Electron
donor–acceptor
(EDA)
complex
photoactivation
strategies
emerged
versatile
sustainable
ways
achieve
bond
formation,
avoiding
challenges
associated
with
previous
methods.
This
work
describes
an
open‐to‐air,
photoinduced,
site‐selective
C−H
thioetherification
from
readily
available
reagents
via
EDA
formation
that
tolerates
wide
range
different
groups.
Moreover,
C(sp
2
)−halogen
remain
intact
using
protocol,
allowing
late‐stage
installation
sulfide
motif
bioactive
scaffolds,
while
yet
modification
through
more
traditional
C−X
cleavage
protocols.
Additionally,
mechanistic
investigations
support
envisioned
scenario.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(8)
Опубликована: Дек. 22, 2022
Efficient
protocols
for
accessing
iodo-substituted
diaryl
and
aryl(vinyl)
sulfides
have
been
developed
using
iodonium
salts
as
reactive
electrophilic
arylation
vinylation
reagents.
The
reactions
take
place
under
transition-metal-free
conditions,
employing
odorless
convenient
sulfur
A
wide
variety
of
functional
groups
are
tolerated
in
the
S-diarylation,
enabling
regioselective
late-stage
application
several
heterocycles
drug
molecules
mild
reaction
conditions.
novel
S-difunctionalization
pathway
was
discovered
vinyliodonium
salts,
which
proceeds
additive-free
conditions
grants
excellent
stereoselectivity
synthesis
sulfides.
one-pot
strategy
combining
diarylation
subsequent
reduction
provided
facile
access
to
electron-rich
thioanilines
a
direct
potential
candidate
derivative.
retained
iodo
group
allows
array
further
synthetic
transformations.
Mechanistic
insights
were
elucidated
by
isolating
key
intermediate,
relevant
energy
profile
substantiated
DFT
calculations.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(20), С. 3413 - 3431
Опубликована: Сен. 12, 2023
Abstract
Due
their
multifaced
applications,
the
access
to
organosulfur
derivatives
in
an
efficient
and
economical
way
is
a
challenge
organic
synthesis.
In
this
context
photochemistry
photocatalysis
play
crucial
role
development
of
innovative
(and
selective)
Carbon‐Sulphur
bond
formation
processes.
The
present
review
aims
collect
most
recent
strategies
achieve
target
under
visible
light
driven
conditions.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(30)
Опубликована: Май 15, 2024
Atropisomers
hold
significant
fascination,
not
only
for
their
prevalence
in
natural
compounds
but
also
biological
importance
and
wide-ranging
applications
as
chiral
materials,
ligands,
organocatalysts.
While
biaryl
heterobiaryl
atropisomers
are
commonly
studied,
the
enantioselective
synthesis
of
less
abundant
heteroatom-linked
non-biaryl
presents
a
formidable
challenge
modern
organic
synthesis.
Unlike
classical
atropisomers,
these
molecules
allow
rotation
around
two
bonds,
resulting
low
barriers
to
enantiomerization
through
concerted
bond
rotations.
In
recent
years
discovery
new
configurationally
stable
rare
scaffolds
such
aryl
amines,
ethers
sulfones
well
innovative
methodologies
control
configuration
have
been
disclosed
literature
constitute
topic
this
minireview.
Chem,
Год журнала:
2024,
Номер
10(9), С. 2901 - 2915
Опубликована: Июнь 27, 2024
The
synthesis
of
organochalcogenides
remains
a
valuable
area
research
due
to
their
widespread
biological
applications,
particularly
in
pharmaceuticals.
Herein,
our
study
details
the
B(C6F5)3-catalyzed
Csp2–H
functionalization
diverse
arenes,
heteroarenes,
and
pharmacophores
with
thiosuccinimides
or
selenosuccinimides,
providing
selective
access
chalcogenated
products.
This
protocol
enables
late-stage
chalcogenation
drug
molecules
such
as
anti-inflammatory
naproxen,
estrogen
steroid
hormone
estradiol
derivatives,
industrially
relevant
trifluoromethylthiolation
reaction.
Furthermore,
this
C–S
coupling
methodology
provides
facile
metal-free
route
synthesize
vortioxetine,
an
antidepressant
drug,
plethora
significant
organic
motifs.
Detailed
NMR,
EPR
analyses,
density
functional
theory
(DFT)
computational
studies
indicate
that
elongation
thiosuccinimide
N–S
bond
is
assisted
by
boron-centered
adduct,
which
then
leads
stable
ion
pair
arene.
analysis
shows
transient
radical
pair,
potentially
off-cycle
species,
not
directly
involved
catalytic
process.
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
365(4), С. 522 - 526
Опубликована: Янв. 31, 2023
Abstract
Copper‐catalyzed
cross‐coupling
reactions
of
α‐bromoaryl
N
H‐sulfoximines
with
elemental
sulfur
lead
to
benzo[
d
][1,3,2]dithiazole‐1‐oxides,
which
represent
a
new
class
three‐dimensional
heterocycles.
The
proceed
under
mild
conditions
showing
good
functional
group
and
heterocycle
tolerance.
By
imination/oxidation,
the
initial
products
can
be
converted
unprecedented
cyclic
sulfonimidamides
derivatives.
Furthermore,
seven‐membered
was
obtained
by
ruthenium‐catalyzed
ring‐expansion
ethyl
propiolate.
magnified
image
Chemistry - An Asian Journal,
Год журнала:
2024,
Номер
19(9)
Опубликована: Фев. 29, 2024
Abstract
In
light
of
the
important
biological
activities
and
widespread
applications
organic
disulfides,
dithiocarbamates,
xanthates,
thiocarbamates
thiocarbonates,
continual
persuit
efficient
methods
for
their
synthesis
remains
crucial.
Traditionally,
preparation
such
compounds
heavily
relied
on
intricate
multi‐step
syntheses
use
highly
prefunctionalized
starting
materials.
Over
past
two
decades,
direct
sulfuration
C−H
bonds
has
evolved
into
a
straightforward,
atom‐
step‐economical
method
organosulfur
compounds.
This
review
aims
to
provide
an
up‐to‐date
discussion
disulfuration,
dithiocarbamation,
xanthylation,
thiocarbamation
thiocarbonation,
with
special
focus
describing
scopes
mechanistic
aspects.
Moreover,
synthetic
limitations
some
these
methodologies,
along
key
unsolved
challenges
be
addressed
in
future
are
also
discussed.
The
majority
examples
covered
this
accomplished
via
metal‐free,
photochemical
or
electrochemical
approaches,
which
alignment
overraching
objectives
green
sustainable
chemistry.
comprehensive
consolidate
recent
advancements,
providing
valuable
insights
dynamic
landscape
strategies
crucial
classes
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(9), С. 2485 - 2493
Опубликована: Янв. 1, 2024
The
challenging
nickel-catalyzed
coupling
of
ortho
-substituted
aryl
triflates
with
thiols
was
accomplished
by
employing
a
versatile
bidentate
ligand,
capable
decoordination
one
phosphorus
atom
during
the
deprotonation
thiol.
Thioethers
and
their
derivatives
play
important
roles
in
synthetic
chemistry,
medicinal
materials
science.
Herein,
we
report
a
hemilabile
P,N-ligand-assisted
gold-catalyzed
C-S
cross-coupling
reaction
of
organoiodides
with
disulfides.
In
this
reaction,
alkyl
or
aryl
disulfides
react
smoothly
vinyl
iodides
to
afford
series
sulfide
good
excellent
yields.
The
robust
capabilities
thioether
synthesis
are
exemplified
by
the
readily
available
easily
handled
reagents
as
well
compatibility
wide
range
functional
groups.
