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,
Год журнала:
2023,
Номер
135(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
A
free-radical
cascade
approach
has
enabled
the
develop-ment
of
a
synthetically
versatile
alkyl–arylation
olefins.
This
transformation
engages
an
excellent
range
olefins,
from
mono-
to
tetrasubstituted,
without
requiring
directing
or
electronically
activating
groups.
Further
synthetic
advantages,
such
as
facile
generation
quaternary
cen-ters
and
introduction
heteroaryl
groups
with
Lewis
basic
nitrogen
atoms,
also
complement
transition-metal-catalyzed
alkyl–arylation.
Vicinal
stereoarrays
were
gener-ated
high
levels
diastereoselectivity.
The
potential
this
was
demonstrated
by
serving
key
step
in
concise
synthesis
oliceridine,
new
painkiller
that
received
FDA
approval
2020.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(17)
Опубликована: Март 20, 2024
Abstract
An
efficient
asymmetric
remote
arylation
of
C(sp
3
)−H
bonds
under
photoredox
conditions
is
described
here.
The
reaction
features
the
addition
radicals
to
a
double
bond
followed
by
site‐selective
radical
translocation
(1,
n
‐hydrogen
atom
transfer)
as
well
stereocontrolled
aryl
migration
via
sulfinyl‐Smiles
rearrangement
furnishing
wide
range
chiral
α
‐arylated
amides
with
up
>99
:
1
er.
Mechanistic
studies
indicate
that
sulfinamide
group
governs
stereochemistry
product
being
rate
determining
step
preceded
kinetically
favored
1,
‐HAT
process.
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.
