Switchable chemoselective aryne reactions between nucleophiles and pericyclic reaction partners using either 3-methoxybenzyne or 3-silylbenzyne
Hongcheng Tan,
Shuxin Yu,
Xiaoling Yuan
и другие.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Апрель 30, 2024
Arynes
are
known
to
serve
as
highly
reactive
benzene-based
synthons,
which
have
gained
numerous
successes
in
preparing
functionalized
arenes.
Due
the
superb
electrophilic
nature
of
these
fleeting
species,
however,
it
is
challenging
modulate
designated
aryne
transformation
chemoselectively,
when
substrates
possess
multiple
competing
reaction
sites.
Here,
we
showcase
our
effort
manipulate
chemoselective
control
between
two
major
types
transformations
using
either
3-methoxybenzyne
or
3-silylbenzyne,
where
nucleophilic
addition-triggered
reactions
and
non-polar
pericyclic
could
be
differentiated.
This
orthogonal
protocol
found
applicable
various
nucleophiles,
i.e.,
imidazole,
N-tosylated/N-alkyl
aniline,
phenol,
alcohol,
an
array
partners,
furan,
cyclopentadiene,
pyrrole,
cycloheptatrienone,
cyclohexene.
Beyond
arylation
reactions,
C-N
bond
insertion,
Truce-Smiles
rearrangement,
annulation
appropriate
modes
well.
Moreover,
this
can
find
potential
synthetic
application.
Язык: Английский
Revisiting the Synthetic Utility of 4,5‐Dehydro[2.2]paracyclophane
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 22, 2024
Abstract
4,5‐Dehydro[2.2]paracyclophane,
an
aryne
species
of
[2.2]paracyclophane
([2.2]PCP)
was
reported
more
than
half
a
century
ago.
However,
despite
its
potential
usefulness
for
preparing
[2.2]PCP
derivatives,
this
is
rarely
considered
in
synthetic
applications,
probably
because
the
efficiency
generation
and
reaction
with
arynophiles
are
low
under
harsh
conditions
classical
methods
involving
precursors.
We
have
prepared
o
‐iodoaryl
triflate‐
‐silylaryl
triflate‐type
precursors
achieved
4,5‐dehydro[2.2]PCP,
which
reacted
diverse
range
to
afford
functionalized
including
[2.2]PCP‐fused
π‐extended
polyaromatics.
Our
results
highlight
utility
historically
overlooked
4,5‐dehydro[2.2]PCP
intermediate.
Язык: Английский
Synthesis of Multisubstituted Aromatics via 3-Triazenylarynes
Organic Letters,
Год журнала:
2023,
Номер
25(38), С. 7030 - 7034
Опубликована: Сен. 15, 2023
An
efficient
method
for
generating
3-triazenylarynes
from
ortho-iodoaryl
triflate-type
precursors
was
developed.
The
generated
arynes
reacted
with
various
arynophiles
high
regioselectivity
because
of
the
triazenyl
group.
3-triazenylaryne
functioned
as
useful
intermediates
diverse
multisubstituted
aromatic
compounds
through
transformation
remaining
group
aryne
adducts
and
group-directed
ortho-C-H
functionalization.
Язык: Английский
Development of 3-triazenylaryne and its application to iterative aryne reactions via o-triazenylarylboronic acids
Chemical Communications,
Год журнала:
2023,
Номер
59(96), С. 14249 - 14252
Опубликована: Янв. 1, 2023
A
novel
aryne
species
3-triazenylaryne
has
been
developed
as
a
divergent
platform
for
the
generation
of
3-alkynylaryne
through
o
-triazenylarylboronic
acids.
Язык: Английский
Regiocontrol Using Fluoro Substituent on 3,6-Disubstituted Arynes
Chemical and Pharmaceutical Bulletin,
Год журнала:
2023,
Номер
71(10), С. 775 - 781
Опубликована: Сен. 30, 2023
The
effect
of
fluoro
substituent
on
the
regioselectivity
several
reactions
3,6-disubstituted
arynes
was
studied.
These
contained
another
inductively
electron-withdrawing
other
than
fluorine.
A
reasonable
degree
regiocontrol
achieved
in
(3
+
2)
cycloaddition
reaction
aryne
containing
both
fluorine
and
bromine
atoms
with
benzyl
azide.
Furthermore,
insertion
into
Sn-F
σ-bonds
three-component
coupling
involving
C=O
π-bonds
also
led
to
high
regiocontrol.
Язык: Английский