Photocatalytic Pyridyl-carbamoylation of Alkenes for Accessing β-Pyridyl Amides
Organic Letters,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 7, 2025
The
β-pyridyl
amide
is
a
critical
scaffold
in
medical
discovery
yet
lacks
efficient
synthetic
methods.
Here,
we
describe,
for
the
first
time,
visible-light-induced,
redox-neutral
radical
cross-coupling
reaction
involving
alkenes,
oxamic
acids,
and
cyanopyridines
that
offers
versatile
assembly
of
β-pyridylamides.
This
approach
features
mild
conditions,
high
step
efficiency,
substrate
breadth,
providing
green
strategy
alkene
pyridyl-carbamoylation.
Achieving
this
transformation
relies
on
catalytic
system,
which
adeptly
avoids
competing
nucleophilic
carbamoyl
with
electrophilic
pyridyl
radical,
enabling
three-component
tandem
process
chemoselectivity.
Язык: Английский
Nickel-Catalyzed C(sp3)–C(sp3) Cross-Coupling of Carboxamides and Unactivated Alkyl Iodides
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 22, 2025
The
construction
of
C(sp3)-C(sp3)
bonds
through
cross-coupling
reactions
unactivated
alkyl
halides
and
C-radical
precursors
presents
a
significant
challenge
in
organic
synthesis.
Herein,
we
report
strategy
for
the
formation
using
as
alkylation
reagents
via
1,5-hydrogen
atom
transfer
(HAT)
process.
proceed
under
mild
conditions,
demonstrating
remarkable
tolerance
diverse
array
functional
groups.
This
method
possesses
potential
to
expand
new
pathways
Язык: Английский
Enantioselective β-C(sp3)–H Nucleophilic Tosylation of Native Amides: A Synthetic Platform for Chiral Methyl Stereocenters
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 31, 2025
Enantioselective
oxygenation
of
unactivated
C(sp3)-H
bonds
via
asymmetric
metalation
remains
an
unsolved
challenge.
Herein
we
report
the
development
a
Pd-catalyzed,
enantioselective
tosylation
native
amides
with
NaOTs
as
nucleophile,
representing
rare
example
C-H
functionalization
nucleophilic
coupling
partner.
High
enantioselectivity
in
this
reaction
is
achieved
by
chiral
monoprotected
amino
sulfonamide
(MPASA)
ligands.
Substantial
enhancement
silver
salt
additives
was
also
observed.
Through
desymmetrization
readily
available
isopropyl
moiety,
structurally
diverse
β-tosylated
bearing
α-methyl
stereocenter
were
obtained
high
yield
and
enantioselectivity,
which
complements
current
enzymatic
method
for
making
Roche
ester
synthon.
The
tosylated
products
are
highly
versatile
building
blocks
further
diversifications
nitrogen,
oxygen,
other
nucleophiles,
thus
providing
platform
constructing
methyl
stereocenters.
Язык: Английский