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.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 16, 2025
Quaternary
carbon
centers
are
widespread
structural
motifs,
thus
representing
extensive
interest
in
organic
synthesis.
We
describe
here
an
efficient
nickel-catalyzed
intermolecular,
Markovnikov-selective
arylation
of
minimally
functionalized
alkenes
with
stable
organoborons,
affording
a
broad
range
cyclic
or
acyclic
quaternary
under
mild
conditions.
The
utilization
the
diimine
ligand
is
critical
for
high
reactivity
and
chemoselectivity.
Furthermore,
using
bulky
chiral
as
Ni
catalyst,
stereocenters
can
be
readily
prepared
levels
enantiocontrol.
Mechanism
studies
suggest
that,
before
protonation,
rare
nickel
shift
from
alkyl
to
aryl
might
occur.
Nature Communications,
Год журнала:
2025,
Номер
16(1)
Опубликована: Янв. 22, 2025
Fatty
acid
peroxygenases
have
emerged
as
promising
biocatalysts
for
hydrocarbon
biosynthesis
due
to
their
ability
perform
C-C
scission,
producing
olefins
-
key
building
blocks
sustainable
materials
and
fuels.
These
enzymes
operate
through
non-canonical
complex
mechanisms
that
yield
a
bifurcated
chemoselectivity
between
hydroxylation
decarboxylation.
In
this
study,
we
elucidate
structural
features
in
P450
decarboxylases
enable
the
catalysis
of
unsaturated
substrates,
expanding
mechanistic
pathways
decarboxylation
reaction.
Combining
X-ray
crystallography,
molecular
dynamics
simulations,
machine
learning,
identified
intricate
rearrangements
within
active
site
Cβ
atom
substrate
approach
heme
iron,
thereby
promoting
oleate
Furthermore,
demonstrate
absence
aromatic
residue
Phe-His-Arg
triad
preserves
alkenes,
providing
distinct
perspective
on
determinants
activity.
Ultimately,
these
findings
production
biohydrocarbons
from
industrial
feedstocks.
This
study
uncovers
pathway
bio-olefin
feedstocks
by
fatty
unconventional
decarboxylation,
paving
way
bio-based
production.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Окт. 4, 2024
The
challenging
synthesis
of
thermodynamic-unfavored
cis-olefins
through
catalytic
cross-coupling
reactions
requires
the
synergistic
interaction
substrate-activating
units
and
configuration-regulating
catalysts.
Successfully
hitting
these
two
birds
with
one
stone,
we
herein
develop
a
convenient
photoredox
access
to
Z-alkenes
from
alkynes
light
alkanes
bifunctional
iron-catalyzed
system
possessing
both
C(sp
Advanced Synthesis & Catalysis,
Год журнала:
2023,
Номер
366(4), С. 593 - 602
Опубликована: Дек. 7, 2023
Abstract
Unactivated
olefins
rank
amongst
the
most
important
feedstocks
in
organic
synthesis.
Their
availability
makes
them
particularly
useful
synthons
for
subsequent
functionalization,
a
catalytic
manner.
Driven
by
popularity
ascribed
nickel
catalysis
as
new
tool
to
rapidly
forge
molecular
architectures
via
one‐or
two‐electron
manifolds,
recent
years
have
witnessed
significant
advances
Ni‐catalyzed
olefin
difunctionalization.
While
1,2‐difunctionalization
or
remote
functionalization
“chain‐walk”
become
mature
disciplines
repurposing
potential
of
building
blocks,
it
was
only
recently
that
extensions
this
chemistry
1,1‐difunctionalization
been
possible.
This
review
summarizes
1,1‐difunctionalization,
holding
considerable
promise
powerful
strategy
our
ever‐growing
synthetic
repertoire.
European Journal of Organic Chemistry,
Год журнала:
2024,
Номер
27(12)
Опубликована: Фев. 14, 2024
Abstract
Hexafluoroisopropanol
(HFIP)
stands
out
as
a
versatile
solvent
in
synthetic
chemists’
repertoire,
facilitating
diverse
array
of
intricate
chemical
reactions.
It
demonstrates
multifaceted
role
that
extends
beyond
conventional
uses
and,
many
cases,
the
mechanism
appears
to
be
complicated.
This
feature
article
elucidates
significance
HFIP
context
Lewis
and
Brønsted
acid‐catalyzed
reactions
with
specific
emphasis
on
regio‐
stereoselective
functionalization
unsaturated
carbon‐carbon
bonds.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
147(2), С. 1667 - 1676
Опубликована: Янв. 7, 2025
We
report
a
Ni-catalyzed
vicinal
alkylarylation
of
unactivated
alkenes
in
γ,δ-
and
δ,ε-alkenylamines
with
aryl
halides
alkylzinc
reagents.
The
reaction
is
enabled
by
amine
coordination
can
use
all
primary,
secondary,
tertiary
amines.
constructs
two
new
C(sp3)-C(sp3)
C(sp3)-C(sp2)
bonds
produces
δ-
ε-arylamines
C(sp3)-branching
at
the
γ-
δ-positions.
A
variety
heteroaryl
iodides
both
primary
secondary
reagents
be
used
as
coupling
carbon
sources.
Mechanistic
studies
suggest
that
cooperative
effect
organic
nitriles
electron-deficient
(EDAs)
ligands.
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.
Great
advances
have
been
made
by
leveraging
high-valent
Pd(II)/Pd(IV)
catalysis
in
the
areas
of
C–H
activation
and
alkene
difunctionalisation,
thus
representing
a
powerful
approach
for
construction
carbon-carbon
carbon-heteroatom
bond.
However,
catalytic
reactions
involving
Ni(II)/Ni(IV)
are
largely
underdeveloped.
Here
we
report
Ni(II)-catalysed
dicarbofunctionalisation
unactivated
alkenes
via
catalysis.
This
protocol
provides
highly
efficient
direct
route
towards
vicinal
substituted
alkanes
using
primary,
secondary,
tertiary
amides,
as
well
secondary
amines
native
directing
group
under
redox-neutral
conditions
that
challenging
to
access
through
conventional
methods.
The
key
success
this
reaction
is
use
bulky
β-diketone
ligand,
which
could
enable
insertion
aryl-Ni(II)
species,
stabilize
alkyl-Ni(II)
species
inhibit
homolytic
cleavage.
features
group,
broad
substrate
scope,
excellent
scalability.
resulting
Weinreb
amide-derived
products
can
be
readily
derivatized
variety
ketones
aldehyde,
fundamentally
useful
synthetic
chemistry.
In
addition,
has
employed
preparation
several
bioactive
compounds,
showcasing
significant
values
our
current
method.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(50), С. 27211 - 27217
Опубликована: Дек. 7, 2023
A
catalytic,
enantioselective
method
for
direct
α-alkylation
of
ketones
with
unactivated
alkyl
halides
is
realized
by
employing
an
α-enolizable
ketone
in
a
nickel-catalyzed
C(sp3)–C(sp3)
cross-coupling
reaction.
The
key
to
the
success
attributed
unique
bimetallic
ligand.
variety
acyclic
and
iodides
can
serve
as
suitable
substrates
under
mild
conditions
generate
chiral
α-quaternary
carbon
stereocenters
high
yields
good
enantioselectivities.
range
transformations
based
on
moiety
are
also
demonstrated
show
potential
application
this
method.
Preliminary
mechanistic
studies
support
dinickel-catalyzed
mechanism.
