Angewandte Chemie,
Год журнала:
2024,
Номер
136(35)
Опубликована: Май 31, 2024
Abstract
Radical
ipso‐
substitution
offers
an
alternative
to
organometallic
approaches
for
biaryl
synthesis,
but
usually
requires
stoichiometric
reagents
such
as
tributyltin
hydride.
Here,
we
demonstrate
that
visible
light
photoredox
catalysis
can
be
used
ipso
‐biaryl
via
a
halogen‐atom
transfer
(XAT)
regime.
Using
amide
substrates
promote
over
unwanted
ortho‐
addition,
smooth
formation
with
no
constraint
on
the
electronic
character
of
migrating
arene
ring.
The
photoreaction
combined
in
one
operation
achieve
formal
arylation
inert
aniline
C−N
bond.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(35)
Опубликована: Май 31, 2024
Radical
ipso-substitution
offers
an
alternative
to
organometallic
approaches
for
biaryl
synthesis,
but
usually
requires
stoichiometric
reagents
such
as
tributyltin
hydride.
Here,
we
demonstrate
that
visible
light
photoredox
catalysis
can
be
used
ipso-biaryl
via
a
halogen-atom
transfer
(XAT)
regime.
Using
amide
substrates
promote
ipso-
over
unwanted
ortho-addition,
smooth
formation
with
no
constraint
on
the
electronic
character
of
migrating
arene
ring.
The
photoreaction
combined
in
one
operation
achieve
formal
arylation
inert
aniline
C-N
bond.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(49)
Опубликована: Окт. 18, 2023
Abstract
Anilines
are
potentially
high‐value
arylating
agents,
but
limited
by
the
low
reactivity
of
strong
C−N
bond.
We
show
that
reactive
intermediate
benzyne
can
be
used
to
both
activate
anilines,
and
set‐up
an
aryl
transfer
reaction
in
a
single
step.
The
does
not
require
any
transition
metal
catalysts
or
stoichiometric
organometallics,
establishes
metal‐free
route
valuable
biaryl
products
functionalizing
aniline
Organic Letters,
Год журнала:
2024,
Номер
26(13), С. 2612 - 2616
Опубликована: Март 21, 2024
We
describe
a
transition
metal-free
approach
to
hindered
3-amino-2-aryl
phenols
through
cascade
nucleophilic
addition
/
Smiles–Truce
rearrangement
of
functionalized
Kobayashi
aryne
precursor.
Under
anionic
conditions,
secondary
alkyl
amines
add
the
intermediate
set
up
an
aryl
transfer
from
neighboring
sulfonate
group.
The
use
sulfonate,
rather
than
more
typical
sulfonamide,
enables
access
phenolic
biaryl
products
that
are
important
motifs
in
natural
and
pharmaceuticals.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(30)
Опубликована: Апрель 29, 2024
Abstract
An
efficient
and
broadly
applicable
rhodium‐catalyzed
direct
ortho
‐arylation
of
anilines
with
aryl
iodides
relying
on
readily
available
aminophosphines
as
traceless
directing
groups
is
reported.
Its
scope
functional
group
compatibility
were
both
found
to
be
quite
broad
a
large
variety
(hetero)aryl
iodides,
including
complex
ones,
could
utilized.
The
‐arylated
obtained
in
high
average
yields,
without
any
competing
diarylation
full
regioselectivity,
which
constitutes
major
step
forward
compared
other
processes.
reaction
moreover
not
limited
an
bromide
triflate
successfully
used,
extended
diarylation.
Mechanistic
studies
revealed
the
key
unique
role
aminophosphine,
acting
only
substrate
but
also
ligand
for
rhodium
catalyst.
A
synthetic
approach
to
dibenzophospholes
was
developed
via
the
gold-
and
copper-catalyzed
annulation
reactions
of
arynes
phosphites.
The
reaction
conditions
demonstrated
a
broad
functional
group
tolerance,
enabling
synthesis
diverse
range
dibenzophosphole
5-oxides.
This
method
is
useful
for
preparing
with
unique
optical
electronic
properties.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 14, 2025
Despite
the
widespread
use
of
arynes
in
organic
synthesis,
their
polymerization
remains
a
significant
challenge
due
to
intrinsic
instability
and
short
lifetime
aryne
intermediates.
Here,
we
report
method
for
using
simple
organonucleophile,
N-arylpyrazole,
as
an
initiator.
This
proceeds
via
unique
pyrazole-induced
nucleophilic
aromatic
substitution
mechanism,
facilitating
formation
poly(ortho-arylene)s
with
narrow
polydispersity
well-defined
structures.
The
high
chemical
stability
N-arylpyrazole
allows
broader
scope
applications,
including
at
side
chain
preformed
polymers
(graft
polymerization)
synthesis
star-shaped
poly(ortho-arylene)s.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(30)
Опубликована: Апрель 29, 2024
Abstract
An
efficient
and
broadly
applicable
rhodium‐catalyzed
direct
ortho
‐arylation
of
anilines
with
aryl
iodides
relying
on
readily
available
aminophosphines
as
traceless
directing
groups
is
reported.
Its
scope
functional
group
compatibility
were
both
found
to
be
quite
broad
a
large
variety
(hetero)aryl
iodides,
including
complex
ones,
could
utilized.
The
‐arylated
obtained
in
high
average
yields,
without
any
competing
diarylation
full
regioselectivity,
which
constitutes
major
step
forward
compared
other
processes.
reaction
moreover
not
limited
an
bromide
triflate
successfully
used,
extended
diarylation.
Mechanistic
studies
revealed
the
key
unique
role
aminophosphine,
acting
only
substrate
but
also
ligand
for
rhodium
catalyst.
