Dearomative 1,4-Difunctionalization of Non-Activated Arenes Enabled by Boryl Radical-Mediated Halogen-Atom Transfer
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 1294 - 1304
Опубликована: Янв. 7, 2025
Given
the
widespread
presence
of
spirocyclic
scaffolds
in
natural
products
and
pharmacologically
relevant
synthetic
compounds,
development
efficient
methodologies
for
their
construction
holds
great
importance
medicinal
chemistry
pharmaceutical
research.
In
this
study,
a
general
photochemical
dearomative
spirocyclization
nonactivated
arenes
has
been
established.
The
key
to
method
lies
ability
amine-borane
radicals
activate
aryl
bromides
iodides
via
halogen-atom
transfer,
thereby
allowing
conversion
halides
into
corresponding
subsequent
chemodivergent
transformations.
remarkable
compatibility
versatility
1,4-difunctionalization
is
showed
by
rapid
assembly
structurally
diverse
1,4-cyclohexadiene-based
spirocycles
incorporating
oxindole,
indoline,
or
dihydrobenzofuran
subunits.
Moreover,
potential
utility
protocol
exemplified
formal
total
synthesis
vasopressin
V2
receptor
antagonist
Satavaptan.
Язык: Английский
Visible-Light-Induced Photoredox Construction of Trifluoromethylated Quaternary All-Carbon Centers and Tertiary Alcohols via C(sp3)–Si Bond Cleavage
Synthesis,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 10, 2024
Abstract
The
construction
of
trifluoromethylated
quaternary
carbon
centers
and
tertiary
alcohols
is
realized
by
organo-photoredox
catalysis.
process
proceeds
via
visible-light-induced
C(sp3)–Si
bond
cleavage
for
the
generation
α-trifluoromethylated
benzyl
radicals,
which
are
readily
trapped
electron-deficient
alkenes
with
excellent
regioselectivity
all-carbon
centers.
α-difluoromethyl
counterparts
also
suitable
this
radical
conjugate
addition.
Furthermore,
in
situ
oxidation
these
radicals
O2
from
air
affords
high
yields,
extends
Fleming–Tamao
reaction
to
systems.
Язык: Английский