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.
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.
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.
Bulletin of the Korean Chemical Society,
Год журнала:
2025,
Номер
46(4), С. 413 - 421
Опубликована: Апрель 1, 2025
Abstract
In
recent
years,
transition
metal‐catalyzed
reductive
alkylation
of
alkenes
has
gained
attention
due
to
its
ability
circumvent
the
use
unstable
organometallic
reagents
by
generating
reactive
intermediates
in
situ
from
stable
precursors
with
enhanced
reaction
safety
and
efficiency.
This
review
provides
an
overview
advancements
copper‐catalyzed
alkenes,
a
particular
focus
on
hydrosilanes
diborons
as
stoichiometric
reducing
agents.
Key
topics
include
mechanistic
insights,
strategies
for
controlling
regio‐
stereoselectivity
both
intra‐
intermolecular
reactions,
innovative
catalyst
designs
selective
product
synthesis.
Emerging
trends
such
radical‐mediated
transformations
contributions
alternative
first‐row
metals
including
nickel
iron
are
also
discussed.
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.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(45), С. 30733 - 30740
Опубликована: Окт. 29, 2024
Aryl-substituted
aliphatic
amines
are
widely
recognized
as
immensely
valuable
molecules.
Consequently,
the
development
of
practical
strategies
for
construction
these
molecules
becomes
increasingly
urgent
and
critical.
Here,
we
have
successfully
achieved
multifunctionalization
reactions
alkenyl
alcohols
in
a
sequential
relay
process,
which
enables
transformation
patterns
arylamination,
deuterated
methylenated
arylamination
to
easy
access
multifarious
arylalkylamines.
Notably,
novel
functionalization
mode
carbonyl
groups
has
been
developed
facilitate
processes
deuterium
incorporation
methylene
introduction,
thereby
providing
new
means
diverse
transformations
groups.
This
methodology
displays
wide
tolerance
toward
functional
groups,
while
also
exhibiting
good
applicability
across
various
skeletal
structures
alkenols
amines.
