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.
ACS Catalysis,
Год журнала:
2022,
Номер
12(14), С. 8511 - 8526
Опубликована: Июль 1, 2022
Alkene
aminoarylation
with
arylsulfonylacetamides
via
a
visible-light
mediated
radical
Smiles-Truce
rearrangement
represents
convenient
approach
to
the
privileged
arylethylamine
pharmacaphore
traditionally
generated
by
circuitous,
multi-step
sequences.
Herein,
we
report
detailed
synthetic,
spectroscopic,
kinetic,
and
computational
studies
designed
interrogate
proposed
mechanism,
including
key
aryl
transfer
event.
The
data
are
consistent
rate-limiting
1,4-aryl
migration
occurring
either
stepwise
process
involving
Meisenheimer-like
intermediate
or
in
concerted
fashion
dependent
on
both
arene
electronics
alkene
sterics.
Our
efforts
probe
mechanism
have
significantly
expanded
substrate
scope
of
transformation
respect
migrating
group
provide
further
credence
synthetic
potential
migrations.
Green Chemistry,
Год журнала:
2024,
Номер
26(11), С. 6774 - 6778
Опубликована: Янв. 1, 2024
A
novel
and
attractive
photochemical
difunctionalization
of
N
-tosyl
acrylamide
for
constructing
alkylsulfonylated
oxindoles
amides
with
excellent
substrate
adaptability
via
a
radical
Smiles
rearrangement
strategy
is
described.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(3)
Опубликована: Ноя. 17, 2022
The
ability
to
construct
C(sp3
)-C(sp3
)
bonds
from
easily
accessible
reagents
is
a
crucial,
yet
challenging
endeavor
for
synthetic
organic
chemists.
Herein,
we
report
the
realization
of
such
cross-coupling
reaction,
which
combines
N-sulfonyl
hydrazones
and
)-H
donors
through
diarylketone-enabled
photocatalytic
hydrogen
atom
transfer
subsequent
fragmentation
obtained
alkylated
hydrazide.
This
mild
metal-free
protocol
was
employed
prepare
wide
array
alkyl-alkyl
cross-coupled
products
tolerant
variety
functional
groups.
application
this
chemistry
further
provides
preparatively
useful
route
various
medicinally-relevant
compounds,
as
homobenzylic
ethers,
aryl
ethyl
amines,
β-amino
acids
other
moieties
are
commonly
encountered
in
approved
pharmaceuticals,
agrochemicals
natural
products.
Chemical Science,
Год журнала:
2024,
Номер
15(11), С. 4031 - 4040
Опубликована: Янв. 1, 2024
A
free-radical
approach
featuring
an
intramolecular
aryl
migration
has
significantly
expanded
the
scope
for
alkyl–(hetero)arylation
of
simple
olefins.
It
was
also
leveraged
as
key
step
in
a
new
synthesis
recently
approved
pharmaceutical.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(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.
