The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(11), С. 8035 - 8040
Опубликована: Май 28, 2024
Mild,
metal-free,
and
operationally
simple
three-component
coupling
reactions
involving
arynes,
phosphites,
acrylates
have
been
achieved.
The
reaction
proceeded
well
with
α-
or
β-substituted
acrylates.
Additionally,
various
functional
groups
were
tolerated
under
these
conditions,
resulting
in
diverse
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(7), С. 1538 - 1544
Опубликована: Фев. 8, 2024
Abstract
Herein
we
report
a
method
for
the
synthesis
of
thioethers
by
forging
C(aryl)‐S
bond
via
an
aryne
mechanism.
The
active
species
can
be
generated
from
o
‐diiodoarenes
and
NaH
in
THF
at
room
temperature,
then
lead
to
arylations
wide
range
aryl
thiols
thioureas.
Different
transition
metal‐catalyzed
cross‐coupling
reactions,
no
disubstituted
byproduct
is
formed
our
protocol.
‐iodoaryl
thioether
products
are
intermediates
that
could
transformed
into
pharmaceutically
interesting
molecules.
Organic Letters,
Год журнала:
2023,
Номер
25(35), С. 6459 - 6463
Опубликована: Авг. 25, 2023
A
straightforward
and
efficient
strategy
for
the
synthesis
of
phosphachromones
has
been
reported
via
insertion
arynes
into
P–O
bonds.
This
operationally
simple
reaction
is
compatible
with
different
functional
groups,
affording
various
by
simultaneous
formation
C–P
C–O
bonds
in
one
step
moderate
to
good
yields,
Fries
rearrangement
involving
phosphorus
atoms
a
key
reaction.
Chinese Journal of Organic Chemistry,
Год журнала:
2023,
Номер
43(2), С. 503 - 503
Опубликована: Янв. 1, 2023
The
three
component
reaction
has
the
advantages
of
simple
operation
and
efficient
reaction,
in
line
with
principles
atomic
economy
green
environmental
protection.At
present,
arylation
without
transition
metal
catalyst
is
mainly
divided
into
types
as
following:
(1)
direct
arylation,
(2)
insertion
aryne
σ-bond
or
π-bond,
(3)
three-component
reactions
involving
aryne.Compared
mechanism
still
unclear,
published
reviews
are
lacking.In
order
to
facilitate
scientific
researchers
consult
understand
involved
aryne,
progresses
recent
years
reviewed.
The Journal of Organic Chemistry,
Год журнала:
2021,
Номер
86(15), С. 10724 - 10746
Опубликована: Июль 8, 2021
Synthetic
methodology
utilizing
two
aryne
intermediates
(i.e.,
a
formal
benzdiyne)
enables
the
rapid
generation
of
structurally
complex
molecules
with
diverse
functionality.
This
report
describes
sequential
ortho-benzyne
for
synthesis
2,3-disubstituted
aryl
phosphonates.
Aryl
phosphonates
have
proven
useful
in
medicinal
chemistry
and
materials
science,
reported
provides
two-step
route
to
functionally
dense
variants
by
way
3-phosphonyl
benzyne
intermediates.
The
process
begins
regioselective
trapping
3-trifloxybenzyne
intermediate
an
O-silyl
phosphite
Abramov-like
reaction
bond
strained
Csp
carbons
phosphorus
silicon.
Standard
aryne-generating
conditions
follow
convert
resulting
2-silylphenyl
triflate
into
benzyne,
which
readily
reacts
numerous
reactants
form
variety
2,3-difunctionalized
phosphonate
products.
DFT
computational
studies
shed
light
on
important
mechanistic
details
revealed
that
benzynes
are
highly
polarizable.
Specifically,
distortion
internal
angles
at
each
atoms
was
strongly
influenced
both
electronegativity
ester
groups
as
well
dielectric
solvation
model.
These
effects
were
verified
experimentally
regioselectivity
benzyl
azide
increased
more
electronegative
esters
and/or
increasingly
polar
solvents.
Conversely,
replacing
conventional
solvent,
acetonitrile,
nonpolar
alternatives
provided
attenuated
or
even
inverted
selectivities.
Overall,
these
showcase
new
reactivity
extend
relay
include
organophosphonates.
Furthermore,
this
work
demonstrates
reactions
could
be
tuned
simply
changing
solvent.
Organic Letters,
Год журнала:
2022,
Номер
24(11), С. 2192 - 2196
Опубликована: Март 14, 2022
An
efficient
and
transition-metal-free
three-component
reaction
with
benzynes
formed
in
situ
from
2-(trimethylsilyl)aryl
triflate,
phosphites,
ketones
was
developed
for
the
synthesis
of
benzoxaphosphole
1-oxides.
array
1-oxides
were
prepared
both
activated
non-activated
moderate
to
good
yields
a
broad
functional
group
tolerance.
This
is
useful
preparing
organophosphorus
compounds
encountered
natural
products
materials.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 1, 2024
We
have
successfully
synthesized
a
series
of
bidentate
ligands
by
utilizing
2-(trimethylsilyl)phenyl
trifluorosulfonate
as
precursor
for
the
benzyl
group.
This
method
proceeded
inserting
polythiourea
into
C═S
π-bond,
intramolecular
ring
proton
migration,
and
opening.
Salient
features
this
strategy
are
mild
reaction
conditions,
novel
product
structure,
excellent
stereochemistry,
good
functional
group
tolerance.
Furthermore,
density
theory
calculations
were
performed
to
gain
insights
transfer
mechanism.
Organic Letters,
Год журнала:
2022,
Номер
24(45), С. 8295 - 8299
Опубликована: Ноя. 7, 2022
An
efficient
and
straightforward
method
for
the
synthesis
of
aryl(alkynyl)phosphinates
was
developed
via
a
three-component
coupling
reaction
involving
arynes,
phosphites,
alkynes.
array
were
produced
from
both
aryl
aliphatic
group-substituted
acetylenes.
This
operationally
simple
is
tolerant
to
many
functional
groups,
affording
various
in
moderate
good
yields.
The
synthetic
utility
alkynyl
phosphinates
afforded
by
this
demonstrated
elaboration
products
into
phosphorus-containing
compounds.