Organic Letters,
Год журнала:
2024,
Номер
26(43), С. 9383 - 9388
Опубликована: Окт. 22, 2024
Herein,
a
direct
transformation
of
aliphatic
C–H
bonds
to
oxime
ethers
has
been
developed
via
light-promoted
hydrogen
atom
transfer
(HAT)
in
the
absence
photocatalyst.
Singlet
oxygen
and
chlorine
radical
are
complementary
C(sp3)–H
bond
cleaving
agents
this
reaction,
enabling
extraction
atoms
from
diverse
range
compounds,
like
cycloalkanes,
ethers,
amines,
amides,
cyclic
sulfides.
This
method
excels
transforming
common
into
valuable
featuring
abundant
chemical
feedstocks,
good
functional
group
tolerance,
catalyst
free
conditions.
Abstract
Thioethers
(sulfides)
play
a
crucial
role
in
therapeutics,
diagnostics,
and
functional
materials.
Traditionally,
their
synthesis
involved
the
use
of
thiols
or
derivatives,
which
are
associated
with
unpleasant
odors
potential
health
risks.
Recently,
significant
research
has
focused
on
employing
oxygenated
sulfur
compounds,
such
as
sulfinates,
sulfonyl
oxyacids,
sulfoxides,
thiol
surrogates
for
thioether
synthesis.
This
review
highlights
recent
advancements
deoxygenative
synthesis,
categorizing
them
by
reaction
types,
including
cross-coupling
reactions,
C–H
functionalization,
hydro/halo/oxy-thiolation
unsaturated
hydrocarbons.
We
also
discuss
representative
mechanisms
to
provide
comprehensive
understanding
these
innovative
approaches.
1
Introduction
2
Cross-Coupling
Reactions
3
Functionalization
4
Hydro/Halo/Oxy-thiolation
Unsaturated
Hydrocarbons
5
Conclusion
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 28, 2025
Carboxylic
acids
are
bench-stable
and
readily
available
chemical
feedstocks
that
function
as
optimal
fundamental
synthetic
platforms
for
the
construction
of
C(sp3)–C(sp3)
bonds
via
decarboxylation
processes.
We
present
a
novel
practical
protocol
decarboxylative
alkylation
Morita–Baylis–Hillman
acetates
with
various
carboxylic
photoinduced
iron-mediated
ligand-to-metal
charge
transfer
(LMCT)
process
under
redox-neutral
conditions.
This
method
exhibits
remarkable
tolerance
to
wide
array
acids,
including
primary,
secondary,
tertiary
obviating
requirement
preactivated
radical
precursors.
The
preliminary
mechanistic
analyses
indicate
pathway
is
involved
in
this
catalytic
transformation.
Chemical Science,
Год журнала:
2024,
Номер
15(30), С. 12077 - 12085
Опубликована: Янв. 1, 2024
Electron
transfer
to
the
2
LMCT
state
of
a
photoactive
complex
based
on
Earth-abundant
iron
has
been
used
drive
photocatalytic
aminomethylation
reactions
by
generation
α-aminoalkyl
radicals
and
underlying
mechanism
investigated.
