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:
2024,
Номер
146(15), С. 10274 - 10280
Опубликована: Апрель 3, 2024
The
construction
of
C(sp3)–C(sp3)
bonds
remains
one
the
most
difficult
challenges
in
cross-coupling
chemistry.
Here,
we
report
a
photoredox/nickel
dual
catalytic
approach
that
enables
simultaneous
formation
two
linkages
via
trimolecular
alkenes
with
alkyl
halides
and
hypervalent
iodine-based
reagents.
reaction
harnesses
bimolecular
homolytic
substitution
(SH2)
mechanism
chemoselective
halogen-atom
transfer
(XAT)
to
orchestrate
regioselective
addition
electrophilic
nucleophilic
radicals
across
unactivated
without
need
for
directing
auxiliary.
Utility
is
highlighted
through
late-stage
(fluoro)alkylation
(trideutero)methylation
C═C
bearing
different
patterns,
offering
straightforward
access
drug-like
molecules
comprising
sp3-hybridized
carbon
scaffolds.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Фев. 17, 2024
Abstract
Transition
metal-catalyzed
reductive
difunctionalization
of
alkenes
with
alkyl
halides
is
a
powerful
method
for
upgrading
commodity
chemicals
into
densely
functionalized
molecules.
However,
super
stoichiometric
amounts
metal
reductant
and
the
requirement
installing
directing
group
to
suppress
inherent
β-H
elimination
bring
great
limitations
this
type
reaction.
We
demonstrate
herein
that
two
different
accessible
via
radical-anion
relay
Na
2
S
O
4
as
both
sulfone-source.
The
together
electron-shuttle
catalyst
crucial
divert
mechanistic
pathway
toward
formation
sulfone
anion
instead
previously
reported
alkylmetal
intermediates.
Mechanistic
studies
allow
identification
carbon-centered
radical
sulfur-centered
radical,
which
are
in
equilibrium
capture
or
extrusion
SO
could
be
converted
accelerated
by
iron
catalysis,
leading
observed
high
chemoselectivity.
Synthesis,
Год журнала:
2023,
Номер
56(01), С. 1 - 15
Опубликована: Июнь 12, 2023
Abstract
Catalytic
enantioselective
1,2-dicarbofunctionalization
(1,2-DCF)
of
alkenes
is
a
powerful
transformation
growing
importance
in
organic
synthesis
for
constructing
chiral
building
blocks,
bioactive
molecules,
and
agrochemicals.
Both
two-
three-component
context,
this
family
reactions
generates
densely
functionalized,
structurally
complex
products
single
step.
Across
several
distinct
mechanistic
pathways
at
play
these
transformations
with
nickel
or
palladium
catalysts,
stereocontrol
can
be
obtained
through
tailored
ligands.
In
Review
we
discuss
the
various
strategies,
mechanisms,
catalysts
that
have
been
applied
to
achieve
enantioinduction
alkene
1,2-DCF.
1
Introduction
2
Two-Component
Enantioselective
1,2-DCF
via
Migratory
Insertion
3
Radical
Capture
4
Three-Component
5
6
Miscellaneous
Mechanisms
7
Conclusion
ACS Catalysis,
Год журнала:
2024,
Номер
14(7), С. 4395 - 4406
Опубликована: Март 8, 2024
Asymmetric
reductive
three-component
arylalkylation
of
alkenes
via
the
radical
relay
method
has
been
well
established,
while
asymmetric
migratory
insertion
strategy
remains
unexplored.
We
report
enantioselective
nickel-catalyzed
cross-electrophile
with
aryl-
and
alkyl
halides
an
integrated
Heck
carbometalation/radical
cross-coupling
sequence.
This
protocol
employing
a
chiral
Ni/PHOX
catalytic
system
allows
terminal
internal
to
successfully
engage
exquisite
control
regio-,
chemo-,
stereoselectivity.
More
importantly,
this
undergoes
regio-
arylnickelation
followed
by
Csp3–Csp3
elimination,
thus
exhibiting
reverse
regioselectivity
method.
Mild
reaction
conditions
exceptional
functional
group
tolerance
facilitate
method's
compatibility
bioactive
motifs
modular
synthesis
biologically
active
compounds.
The
experiments
density
theory
calculations
provide
insights
into
mechanism
origin
stereoselectivity,
hemilabile
nature
PHOX
ligand
is
critical
for
achieving
arylalkylation.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 17, 2025
1,2-Amino-difunctionalization
reactions
of
alkenes
allow
the
efficient
introduction
different
functional
groups
and
rapid
construction
valuable
functionalized
amines.
In
this
respect,
we
report
a
copper-catalyzed
1,2-amino-alkoxycarbonylation
unactivated
with
CO
alkylamine
precursors
in
presence
Lewis
acid
additive.
The
novel
protocol
allows
direct
access
to
β-amino
derivatives
from
easily
available
starting
materials.
presented
methods
feature
high
chemo-
regioselectivities,
good
group
tolerance,
substrate
scope
including
diverse
bioactive
compounds
drug-like
molecules.
Mechanistic
studies
indicate
that
additive
is
key
realizing
umpolung
addition
nucleophilic
aminyl
radicals
electron-rich
alkenes,
which
represents
an
elegant
activation
strategy
for
radicals.
Chemical Science,
Год журнала:
2025,
Номер
16(10), С. 4442 - 4449
Опубликована: Янв. 1, 2025
Catalytic
methods
by
switching
the
least
parameters
for
regioselective
and
site-divergent
transformations
to
construct
different
architectures
from
identical
readily
available
starting
materials
are
among
most
ideal
catalytic
protocols.
However,
associated
challenge
precisely
control
both
regioselectivity
site
diversity
renders
this
strategy
appealing
yet
challenging.
Herein,
Ni-catalyzed
cross-electrophile
1,2-
1,3-arylalkylations
of
N-acyl
allylic
amines
have
been
developed.
This
reductive
three-component
protocol
enables
1,2-arylalkylation
1,3-arylalkylation
with
aryl
halides
alkyl
excellent
chemo-,
regio-
site-selectivity,
representing
first
example
controlled
migratory
difunctionalization
alkenes
under
conditions.
A
wide
range
terminal
internal
unactivated
amines,
precursors
were
tolerated,
providing
straightforward
efficient
access
diverse
C(sp3)-rich
branched
aliphatic
materials.
Abstract
Asymmetric
multicomponent
reactions
are
considered
as
efficient
protocols
for
constructing
complex
chiral
molecules
because
of
their
step‐
and
atom‐economy.
Nickel‐catalyzed
asymmetric
three‐component
dicarbofunctionalization
alkenes
has
been
well
developed
in
recent
years,
which
is
used
the
area
total
synthesis
natural
products
late‐stage
modification
drugs
rapid
incorporation
sp
3
‐enriched
carbon
centers.
In
this
concept,
significant
breakthroughs
field
summarized,
together
with
related
mechanisms.
Moreover,
remaining
challenges
potential
opportunities
also
highlighted.
Advanced Materials,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 18, 2024
Abstract
For
traditional
metal
complexes,
intricate
chemistry
is
required
to
acquire
appropriate
ligands
for
controlling
the
electron
and
steric
hindrance
of
active
centers.
Comparatively,
preparation
single‐atom
catalysts
much
easier
with
more
straightforward
effective
accesses
arrangement
control
The
presence
coordination
atoms
or
neighboring
functional
on
supports'
surface
ensures
stability
single‐atoms
their
interactions
individual
substantially
regulate
performance
Therefore,
collaborative
interaction
between
surrounding
environment
enhances
initiation
reaction
substrates
formation
transformation
crucial
intermediate
compounds,
which
imparts
significant
catalytic
efficacy,
rendering
them
a
valuable
framework
investigating
correlation
structure
activity,
as
well
mechanism
in
organic
reactions.
Herein,
comprehensive
overviews
both
homogeneous
complexes
reactions
are
provided.
Additionally,
reflective
conjectures
about
advancement
synthesis
also
proposed
present
reference
later
development.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(36)
Опубликована: Июнь 13, 2024
Isotopically
labeled
alkanes
play
a
crucial
role
in
organic
and
pharmaceutical
chemistry.
While
some
deuterated
methylating
agents
are
readily
available,
the
limited
accessibility
of
other
deuteroalkyl
reagents
has
hindered
synthesis
corresponding
products.
In
this
study,
we
introduce
nickel-catalyzed
system
that
facilitates
various
deuterium-labeled
through
hydrodeuteroalkylation
d2-labeled
alkyl
TT
salts
with
unactivated
alkenes.
Diverging
from
traditional
reagents,
thianthrenium
(TT)
can
effectively
selectively
deuterium
at
α
position
chains
using
D