A
nickel-catalyzed
intermolecular
three-component
1,1-difunctionalization
of
unactivated
alkenes
with
quinoxaline/naphthoquinone
and
arylboronic
acids
via
organometallic-radical
relay
is
developed.
This
efficient
protocol
provides
a
new
method
to
access
variety
arylalkanes
in
moderate
good
yields
broad
substrate
scope
excellent
functional
group
tolerance.
The
mechanistic
studies
provide
insights
into
the
mechanism
origin
chemo-
regioselectivity
as
well
confirm
generation
functionalized
benzylic
radicals.
Organic & Biomolecular Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
Selenium-based
catalysts
have
recently
been
utilized
to
facilitate
a
variety
of
new
organic
transformations,
owing
their
intrinsic
advantages,
including
low
cost,
toxicity,
stability
in
both
air
and
water,
strong
compatibility
with
diverse
functional
groups.
The
difunctionalization
alkenes-the
process
incorporating
two
groups
onto
carbon-carbon
double
bond-has
garnered
particular
interest
within
the
chemical
community
its
significant
applications
synthesis.
Recently,
organoselenium-catalyzed
alkenes
has
emerged
as
an
ideal
powerful
route
obtain
high-value
vicinal
difunctionalized
molecules.
This
review
emphasizes
recent
advancements
this
rapidly
evolving
field,
focusing
on
scope,
limitations,
mechanisms
various
reactions.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 25, 2025
A
nickel-catalyzed,
branched-selective
hydroalkylation
of
alkenes
using
diazo
compounds
has
been
developed.
This
protocol
enables
the
functionalization
both
activated
and
unactivated
alkenes,
in
directed
nondirected
manners.
Mono-,
di-,
trisubstituted
can
be
effectively
transformed.
Highly
diastereoselective
hydroalkylations
have
also
demonstrated.
The
method
provides
a
novel
approach
for
introducing
an
α-carbonyl
moiety
to
which
is
currently
inaccessible
by
existing
methods.
Preliminary
mechanistic
investigations
suggest
carbene-type
mechanism,
unusual
nickel
catalysis.
Angewandte Chemie International Edition,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 10, 2025
We
report
for
the
first
time
a
photoinduced
domino
1,1-dicarboxylation
of
alkynes
synthesis
malonic
acid
derivatives
using
cesium
formate
solution
(80%
w/w
in
water),
which
is
different
from
previous
1,2-dicarboxylation
methods
that
usually
produce
succinic
acids.
Cesium
malonate
precipitated
directly
diluted
reaction
mixture
and
was
collected
by
filtration
without
further
purification.
Interestingly,
solid
with
additional
water
led
to
mono-carboxylation
product.
The
solubility
alkaline
environment
are
two
key
factors
contributing
outcome.
A
series
acids,
propionic
acids
drug
intermediates
were
synthesized
good
yields.
Mechanism
experiments
DFT
calculations
indicate
formed
through
α-selective
addition
CO2
•-
cinnamate
intermediate.
This
method
enables
direct
preparation
water-soluble
carboxylate-functionalized
molecules
polymers
hydrophobic
alkyne-containing
precursors,
showing
potential
usability
photolithography
semiconductor
manufacturing.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(16), С. 11682 - 11692
Опубликована: Авг. 1, 2024
Alkene
difunctionalization
is
a
very
attractive
tool
in
synthetic
organic
chemistry.
Herein,
we
disclose
an
operationally
and
practically
simple
method
to
access
2-hydroxytrifluoroethylacetophenones
from
styrene
derivatives
via
photoredox
catalysis.
This
light-mediated
transformation
promotes
the
generation
of
1-hydroxy-2,2,2-trifluoroethyl
carbon-centered
radical
as
key
synthon,
which
undergoes
Giese
addition
with
styrenes
followed
by
Kornblum
oxidation
process.
The
presented
not
only
mild
cost-effective,
but
also
utilizes
photocatalyst
DMSO
oxidant.
Experimental
investigations
support
operative
mechanism
net-neutral
radical/polar
crossover.
ACS Catalysis,
Год журнала:
2024,
Номер
unknown, С. 907 - 916
Опубликована: Дек. 30, 2024
Catalytic
reactions
involving
1,n-metal
migration
provide
a
powerful
approach
for
the
synthesis
of
complex
molecular
skeletons
from
simple
precursors
through
activation
unreactive
bonds.
In
this
work,
nickel-catalyzed
3,3-disubstituted
1-silaindanes,
silicon
analogues
valuable
indanes,
was
developed
by
reaction
1,5-nickel
via
C–H
bond
and
1,4-nickel
C–Si
activation.
It
found
that
not
only
enabled
at
remote
position
but
also
controlled
regioselectivity
subsequent
alkene
insertion.
The
detailed
mechanism
investigated
conducting
deuterium
labeling
experiments
DFT
calculations.
results
obtained
here
demonstrate
high
potential
catalytic
nickel
migrations
activations
useful
cyclic
organosilicon
compounds.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(15), С. 10796 - 10804
Опубликована: Июль 19, 2024
Catalytic
difunctionalization
with
the
direct
activation
of
(O)P-H
bonds
has
been
recently
established
as
a
potentially
robust
platform
to
generate
valuable
organophosphorus
compounds.
In
terms
1,3-enynes,
despite
various
catalytic
methods
developed
for
hydrophosphorylation,
radical-mediated
hetero-functionalization
two
different
atoms
less
explored.
this
study,
we
disclosed
an
electrochemically
induced
hydroxyphosphorylation
1,3-enynes
construction
phosphinyl-substituted
propargyl
alcohols.
The
system
involves
both
arylphosphine
oxides
and
oxygen
in
ambient
air
no
external
metal
or
additive
needed.
use
electrochemistry
ensures
regioselective,
atom-economic
eco-friendly
process.
This
strategy
highlights
advantages
mild
reaction
conditions,
readily
available
starting
materials
broad
substrate
scope,
showing
its
practical
synthetic
value
organic
synthesis.
Synlett,
Год журнала:
2024,
Номер
35(19), С. 2246 - 2250
Опубликована: Авг. 7, 2024
Abstract
A
Fe(OTf)3
and
γ-cyclodextrin-catalyzed
hydroarylation
of
alkenes
with
1-naphthols
or
2-naphthols
is
demonstrated.
This
efficient
general
method
delivers
a
wide
range
benzylic
naphthols
from
readily
available
starting
materials
high
chemo-
regioselectivity
in
up
to
99%
yield,
no
need
for
strong
base
additive.
