Organic Letters,
Год журнала:
2024,
Номер
26(34), С. 7155 - 7160
Опубликована: Авг. 21, 2024
Thiophosphates
serve
as
pivotal
reagents
within
the
realms
of
both
organic
and
inorganic
synthesis,
with
their
most
notable
applications
observed
in
agricultural
chemistry.
This
manuscript
delineates
a
modular
three-component
synthetic
strategy
for
site-selective
arene
C–H
thiophosphorylation
thianthrenium
salt,
1,4-diazabicyclo[2.2.2]octane-sulfur
dioxide
(DABSO),
diarylphosphine
oxides
substrates.
approach
facilitates
metal-free
green
synthesis
diverse
spectrum
S-aryl
phosphorothioates
through
functionalization
late-stage
modification
showcasing
practicality
broad
applicability.
Green Chemistry,
Год журнала:
2024,
Номер
26(17), С. 9371 - 9377
Опубликована: Янв. 1, 2024
Defluorinative
alkylation
and
arylation
between
thianthrenium
salts
α-trifluoromethyl
alkene
to
afford
gem
-difluoroolefins
by
easily
recycling
thianthrene
under
visible
light
irradiation
free
of
metal
photocatalyst.
Organic Letters,
Год журнала:
2024,
Номер
26(31), С. 6652 - 6657
Опубликована: Июль 26, 2024
We
report
a
visible-light-promoted
cyclization/sulfonylation
cascade
of
N-heterocycles
with
thianthrenium
salts
using
DABSO
as
the
SO2
surrogate.
This
method
features
excellent
functional
group
tolerance,
wide
substrate
scope,
and
late-stage
elaboration
bioactive
relevant
molecules.
Mechanistic
investigations
reveal
that
photoactive
electron
donor–acceptor
(EDA)
complexes
between
DABCO
are
capable
generation
aryl
radicals,
which
induce
following
insertion
by
attacking
DABSO,
thus
triggering
key
radical
cyclization
step.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(27)
Опубликована: Май 13, 2024
Abstract
The
construction
of
bicyclo[1.1.1.]pentanes
(BCPs)
typically
require
the
cumbersome
use
labile
[1.1.1.]propellane
in
solution
and
involve
multicomponent
radical
reactions,
which
commonly
produce
undesired
by‐products
that
hinder
efficient
BCPs.
In
this
paper,
we
present
a
catalyst‐free
strategy
by
constructing
an
electron
donor‐acceptor
(EDA)
complex
utilizing
naturally
electron‐deficient
nature
BCP
thianthrenium
salt,
were
irradiated
with
visible
light
to
obtain
trifluoromethyl‐BCP
radicals
through
SET
process,
subsequently
reacted
various
substituted
quinoxalines.
Moreover,
successful
structural
modification
drug
molecule
derivatives
confirm
utility
scheme
field
discovery.
The
synthesis
of
the
hindered
and
polyfluorinated
dialkyl
ethers
poses
challenges
owing
to
bulkiness
tertiary
alcohols
low
nucleophilicity
alcohols.
Additionally,
associated
competitive
side
reactions
always
provide
poor
reactivities.
Although
certain
strategies,
such
as
electrocatalytic
decarboxylation
hydroalkoxylation,
have
been
explored,
a
straightforward
method
for
obtaining
with
structural
diversity
remains
elusive.
In
this
study,
we
proposed
photoinduced
approach
that
involved
in-situ
formation
singlet
carbenes
followed
by
O-H
insertions
access
ethers.
This
successfully
converted
diverse
congested
into
their
corresponding
challenging
Moreover,
other
nucleophiles
phenols,
H2O,
thiols,
silanols,
tributyltin
hydride
etc.
were
tolerable
obtain
valuable
products.
gram-scale
marketed
drugs
modification
complex
molecules
demonstrated
practicality
approach.
detailed
mechanistic
studies
elucidated
key
intermediates
reaction
mechanisms.
