Catalytic photoinduced deoxygenation via B(C6F5)3-enabled OAT for aromatic C−H amination of alkylarenes
Abstract
The
catalytic
deoxygenation
of
N
−
OH
bonds
to
generate
N-centered
radicals
remains
a
significant
challenge
due
the
high
bond
dissociation
energy
and
reliance
on
stoichiometric
auxiliaries
or
activators.
Herein,
we
report
B(C6F5)3-catalyzed
photoinduced
strategy
that
enables
direct
aromatic
C(sp²)
H
amination
alkylarenes
using
N -hydroxyphthalimides
(NHPIs)
as
nitrogen
sources.
Mechanistic
studies
reveal
in
situ
formation
PhthN
O−B(C6F5)3
anion
intermediate
facilitates
an
unusual
transfer
(EnT)-mediated
O
homolysis,
generating
phthalimidyl
radical
(PhthN•)
while
regenerating
borane
catalyst.
This
method
overrides
conventional
preference
for
benzylic
C
oxidation,
achieving
exclusive
with
broad
substrate
scope,
including
electron-rich/poor
alkylarenes,
heteroarenes,
biomolecules.
protocol
operates
under
mild
conditions,
avoids
organic
auxiliaries/activators,
produces
H₂O
sole
byproduct,
thus,
making
it
promising
option
supplant
existing
strategies
arene
amination.
Applications
in
late-stage
functionalization
pharmaceuticals
synthesis
nilotinib
precursor
highlight
its
synthetic
utility.
study
establishes
B(C6F5)3
versatile
oxygen
atom
(OAT)
reagent
photochemistry,
opening
avenues
sustainable
generation.
Research Square (Research Square), Год журнала: 2025, Номер unknown
Опубликована: Апрель 7, 2025
Язык: Английский