Hydrodealkenylative C(sp3)–C(sp2) Bond Fragmentation Using Isayama–Mukaiyama Peroxidation
Jeremy H. Dworkin,
Zhuoxi M. Chen,
Kathleen C. Cheasty
и другие.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 15, 2025
Advancements
in
radical
capture
strategies
have
expanded
the
range
of
products
accessible
from
alkenes
through
dealkenylative
synthesis.
These
methods,
however,
are
still
limited,
as
they
rely
on
ozonolysis
to
generate
key
peroxide
intermediates
alkenes.
Ozonolysis
has
several
limitations.
It
is
not
compatible
with
containing
electron-rich
aromatics.
also
inapplicable
certain
alkene
substitution
patterns
context
Additionally,
it
struggles
sterically
hindered
alkenes,
internal
nucleophiles
and
electrophiles,
allylic
alcohols.
In
this
paper,
using
Isayama-Mukaiyama
peroxidation
(IMP),
we
address
limitations
rescue
previously
inaccessible
substrates
broaden
applicability
functionalization.
particular,
apply
IMP
hydrodealkenylation
describe
a
novel
hydrogenation
condition─employing
catalytic
[FeIII],
benzenethiol,
γ-terpinene
refluxing
methanol─to
resolve
β-scission
issues
associated
IMP-generated
alkyl
silylperoxides.
Язык: Английский
Synthetic utility of functionalized alkylsilyl peroxides for Fe-catalyzed and visible-light-promoted radical transformation
Chemical Science,
Год журнала:
2024,
Номер
15(13), С. 4757 - 4762
Опубликована: Янв. 1, 2024
α-Keto-,
β-acetoxy-
and
β-amidoalkylsilyl
peroxides
are
prepared
from
various
precursors
utilized
for
Fe-catalyzed
visible-light-promoted
radical
functionalization
with
coupling
partners
under
mild
conditions
a
broad
substrate
scope.
Язык: Английский
Copper‐Catalyzed Asymmetric Radical 1,2‐Alkylesterification of 1,3‐Dienes with Cycloalkyl Hydroperoxides and Acids
ChemCatChem,
Год журнала:
2023,
Номер
15(23)
Опубликована: Окт. 17, 2023
Abstract
Transition‐metal‐catalyzed
radical
relay
cross‐coupling
reactions
of
1,3‐dienes
have
recently
emerged
as
one
the
most
powerful
methods
for
construction
structurally
diverse
allylic
compound
in
a
single
chemical
step.
However,
there
still
has
been
limited
success
expanding
substrate
scope
precursors
and
coupling
partners,
well
exploring
catalytic
asymmetric
variants.
Herein,
we
report
copper‐catalyzed
enantioselective
three‐component
1,2‐alkylesterification
using
cycloalkyl
hydroperoxides
carbonyl‐containing
alkyl
sources
carboxylic
acids
O‐nucleophiles
under
mild
redox‐neutral
conditions.
This
protocol
features
broad
good
functional
group
tolerance
with
respect
to
each
component,
providing
practical
access
variety
distally
keto‐functionalized
esters
high
enantioselectivity.
Mechanistic
studies
suggest
involvement
sequential
C−O
this
reaction.
Язык: Английский
Carbon-Chain Elongation by Co-Catalyzed Selective C–C Bond Cleavage and Subsequent Silylperoxylation of Alkene Substrates
ACS Catalysis,
Год журнала:
2024,
Номер
unknown, С. 14754 - 14761
Опубликована: Сен. 20, 2024
Язык: Английский
A copper-catalyzed direct C(sp2)–H alkylsulfonylation of alkenes using alkylsilyl peroxides and DABCO·(SO2)2
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(19), С. 4821 - 4826
Опубликована: Янв. 1, 2023
A
copper-catalyzed
C(sp
2
)–H
alkylsulfonylation
of
alkenes
using
alkylsilyl
peroxides
as
the
alkyl
radical
precursors
with
insertion
sulfur
dioxide
was
developed,
and
shown
to
provide
a
convenient
route
diverse
(
E
)-alkylsulfonyl
alkenes.
Язык: Английский
Facile Generation of Trideuteromethyl Radical from Alkylsilyl Peroxide and Subsequent Functionalization
Asian Journal of Organic Chemistry,
Год журнала:
2024,
Номер
13(11)
Опубликована: Авг. 23, 2024
Abstract
Cu‐
and
Fe‐
catalyzed
trideuteromethylation
reactions
using
alkylsilyl
peroxide
as
trideuteromethyl
radical
precursor
are
reported.
The
was
synthesized
from
acetone‐d6
in
a
three‐step
sequence,
the
with
various
coupling
partners
afforded
efficiently
corresponding
N−CD
3
,
O−CD
C−CD
bond
formation
products.
heptadeuteriopropylation
prepared
butyric
acid‐d7
is
also
described.
Язык: Английский