Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: July 19, 2024
Abstract
Visible-light
photocatalysis
has
evolved
as
a
powerful
technique
to
enable
controllable
radical
reactions.
Exploring
unique
photocatalytic
mode
for
obtaining
new
chemoselectivity
and
product
diversity
is
of
great
significance.
Herein,
we
present
photo-induced
chemoselective
1,2-diheteroarylation
unactivated
alkenes
utilizing
halopyridines
quinolines.
The
ring-fused
azaarenes
serve
not
only
substrate,
but
also
potential
precursors
halogen-atom
abstraction
pyridyl
generation
in
this
photocatalysis.
As
complement
metal
catalysis,
process
with
mild
redox
neutral
conditions
assembles
two
different
heteroaryl
groups
into
regioselectively
contribute
broad
substrates
scope.
obtained
products
containing
aza-arene
units
permit
various
further
diversifications,
demonstrating
the
synthetic
utility
protocol.
We
anticipate
that
protocol
will
trigger
advancement
alkyl/aryl
halides
activation.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
52(9), P. 2946 - 2991
Published: Jan. 1, 2023
This
review
discusses
the
applications
of
N-heterocyclic
carbene
ligands
and
their
influence
on
reactivity
selectivity
Ni-catalysed
alkene
functionalisations.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(17)
Published: Feb. 24, 2023
Precisely
introducing
two
similar
functional
groups
into
bulk
chemical
alkenes
represents
a
formidable
route
to
complex
molecules.
Especially,
the
selective
activation
of
electrophiles
is
in
crucial
demand,
yet
challenging
for
cross-electrophile-coupling.
Herein,
we
demonstrate
redox-mediated
electrolysis,
which
aryl
nitriles
are
both
radical
precursors
and
redox-mediators,
enables
an
intermolecular
alkene
1,2-diarylation
with
remarkable
regioselectivity,
thereby
avoiding
involvement
transition-metal
catalysts.
This
transformation
utilizes
cyanoarene
anions
activating
various
halides
(including
iodides,
bromides,
even
chlorides)
affords
adducts
up
83
%
yield
>20
:
1
regioselectivity
more
than
80
examples,
providing
feasible
approach
bibenzyl
derivatives.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(15), P. 10274 - 10280
Published: April 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,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Feb. 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.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(4), P. 2351 - 2357
Published: Jan. 17, 2024
Cross-coupling
catalysts
typically
react
and
unite
functionally
distinct
partners
via
sequential
inner-sphere
elementary
steps:
coordination,
migratory
insertion,
reductive
elimination,
etc.
Here,
we
report
a
single
catalyst
that
cross-couples
styrenes
benzyl
bromides
iterative
outer-sphere
metal–ligand-carbon
interactions.
Each
partner
forms
stabilized
radical
intermediate,
yet
heterocoupled
products
predominate.
The
system
is
redox-neutral
and,
thus,
avoids
exogenous
oxidants,
resulting
in
simple
scalable
conditions.
Numerous
variations
of
alkene
hydrobenzylation
are
made
possible,
including
access
to
the
privileged
heterodibenzyl
(1,2-diarylethane)
motif
challenging
quaternary
carbon
variants.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(18), P. 8389 - 8398
Published: April 28, 2022
Enantioselective
transformations
of
olefins
are
among
the
most
important
strategies
for
asymmetric
synthesis
organic
compounds.
Chemo-,
diastereo-,
and
stereoselective
control
reactions
with
internal
acyclic
alkenes
construction
functionalized
alkanes
still
remain
a
persistent
challenge.
Here,
we
report
palladium-catalyzed
regiodivergent
Heck-type
diarylation
alkenes.
The
1,2-diarylation
two
accessible
alkenes,
cinnamyl
carbamates
enamides
diazonium
salts
aromatic
boronic
acids,
furnishes
products
containing
vicinal
stereogenic
centers
via
stereospecific
formation
carbonyl
coordination-assisted
transient
palladacycles.
Moreover,
migratory
enables
incontiguous
stereocenters
by
an
interrupted
diastereoselective
1,3-chain-walking
process.
This
protocol
streamlines
access
to
highly
multisubstituted
enantioenriched
amine
derivatives
which
embedded
in
key
biologically
active
motifs.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(13)
Published: Jan. 31, 2023
Transition-metal
catalyzed
intermolecular
1,2-diarylation
of
electronically
unactivated
alkenes
has
emerged
as
an
extensive
research
topic
in
organic
synthesis.
However,
most
examples
are
mainly
limited
to
terminal
alkenes.
Furthermore,
transition-metal
asymmetric
still
remains
unsolved
and
is
a
formidable
challenge.
Herein,
we
describe
highly
efficient
directed
nickel-catalyzed
reductive
internal
with
high
diastereoselectivities.
More
importantly,
our
further
effort
towards
enantioselective
the
challenging
achieved,
furnishing
various
polyarylalkanes
featuring
benzylic
stereocenters
yields
good
enantioselectivities
Interestingly,
generation
cationic
Ni-catalyst
by
adding
alkali
metal
fluoride
key
increased
efficiency
this
reaction.
