Nature Communications,
Journal Year:
2020,
Volume and Issue:
11(1)
Published: Jan. 21, 2020
Abstract
Cross-coupling
reactions
have
developed
into
powerful
approaches
for
carbon–carbon
bond
formation.
In
this
work,
a
Ni-catalyzed
migratory
Suzuki–Miyaura
cross-coupling
featuring
high
benzylic
or
allylic
selectivity
has
been
developed.
With
method,
unactivated
alkyl
electrophiles
and
aryl
vinyl
boronic
acids
can
be
efficiently
transferred
to
diarylalkane
allylbenzene
derivatives
under
mild
conditions.
Importantly,
chlorides
also
successfully
used
as
the
coupling
partners.
To
demonstrate
applicability
of
we
showcase
that
strategy
serve
platform
synthesis
terminal,
partially
deuterium-labeled
molecules
from
readily
accessible
starting
materials.
Experimental
studies
suggest
products
are
generated
Ni(0/II)
catalytic
cycle.
Theoretical
calculations
indicate
chain-walking
occurs
at
neutral
nickel
complex
rather
than
cationic
one.
addition,
original-site
obtained
by
alternating
ligand,
wherein
formation
rationalized
radical
chain
process.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(4), P. 2081 - 2087
Published: Jan. 23, 2023
Substantial
advances
in
enantioconvergent
C(sp3)-C(sp3)
bond
formations
have
been
made
with
nickel-catalyzed
cross-coupling
of
racemic
alkyl
electrophiles
organometallic
reagents
or
nickel-hydride-catalyzed
hydrocarbonation
alkenes.
Herein,
we
report
an
unprecedented
enantioselective
reductive
by
the
direct
utilization
two
different
halides
dual
nickel/photoredox
catalysis
system.
This
highly
selective
coupling
α-chloroboronates
and
unactivated
iodides
furnishes
chiral
secondary
boronic
esters,
which
serve
as
useful
important
intermediates
realm
organic
synthesis
enable
a
desirable
protocol
to
fast
construction
enantioenriched
complex
molecules.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: April 22, 2023
Here,
we
report
an
asymmetric
electrochemical
organonickel-catalyzed
reductive
cross-coupling
of
aryl
aziridines
with
iodides
in
undivided
cell,
affording
β-phenethylamines
good
to
excellent
enantioselectivity
broad
functional
group
tolerance.
The
combination
cyclic
voltammetry
analysis
the
catalyst
reduction
potential
as
well
electrode
study
provides
a
convenient
route
for
reaction
optimization.
Overall,
high
efficiency
this
method
is
credited
electroreduction-mediated
turnover
nickel
instead
metal
reductant-mediated
turnover.
Mechanistic
studies
suggest
radical
pathway
involved
ring
opening
aziridines.
statistical
serves
compare
different
design
requirements
photochemically
and
electrochemically
mediated
reactions
under
type
mechanistic
manifold.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(12), P. 5884 - 5893
Published: Feb. 29, 2020
Cross-electrophile
coupling
(XEC)
of
alkyl
and
aryl
halides
promoted
by
electrochemistry
represents
an
attractive
alternative
to
conventional
methods
that
require
stoichiometric
quantities
high-energy
reductants.
Most
importantly,
electroreduction
can
readily
exceed
the
reducing
potentials
chemical
reductants
activate
catalysts
with
improved
reactivities
selectivities
over
systems.
This
work
details
mechanistically-driven
development
electrochemical
methodology
for
XEC
utilizes
redox-active
shuttles
developed
energy-storage
community
protect
reactive
from
overreduction.
The
resulting
electrocatalytic
system
is
practical,
scalable,
broadly
applicable
reductive
a
wide
range
aryl,
heteroaryl,
or
vinyl
bromides
primary
secondary
bromides.
impact
overcharge
protection
as
strategy
electrosynthetic
methodologies
underscored
dramatic
differences
in
yields
reactions
added
redox
(generally
>80%)
those
without
<20%).
In
addition
excellent
substrates,
protected
overreduction
be
performed
at
high
currents
on
multigram
scales.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(24), P. 9527 - 9533
Published: March 19, 2020
Abstract
Self‐sustained
Ni
I/III
cycles
are
established
as
a
potentially
general
paradigm
in
photoredox
Ni‐catalyzed
carbon–heteroatom
cross‐coupling
reactions
through
strategy
that
allows
us
to
recapitulate
photoredox‐like
reactivity
the
absence
of
light
across
wide
range
substrates
amination,
etherification,
and
esterification
aryl
bromides,
latter
which
has
remained,
hitherto,
elusive
under
thermal
catalysis.
Moreover,
accessibility
is
especially
notable
because
previous
mechanistic
studies
on
this
transformation
conditions
have
unanimously
invoked
energy‐transfer‐mediated
pathways.
Nature Communications,
Journal Year:
2020,
Volume and Issue:
11(1)
Published: Jan. 21, 2020
Abstract
Cross-coupling
reactions
have
developed
into
powerful
approaches
for
carbon–carbon
bond
formation.
In
this
work,
a
Ni-catalyzed
migratory
Suzuki–Miyaura
cross-coupling
featuring
high
benzylic
or
allylic
selectivity
has
been
developed.
With
method,
unactivated
alkyl
electrophiles
and
aryl
vinyl
boronic
acids
can
be
efficiently
transferred
to
diarylalkane
allylbenzene
derivatives
under
mild
conditions.
Importantly,
chlorides
also
successfully
used
as
the
coupling
partners.
To
demonstrate
applicability
of
we
showcase
that
strategy
serve
platform
synthesis
terminal,
partially
deuterium-labeled
molecules
from
readily
accessible
starting
materials.
Experimental
studies
suggest
products
are
generated
Ni(0/II)
catalytic
cycle.
Theoretical
calculations
indicate
chain-walking
occurs
at
neutral
nickel
complex
rather
than
cationic
one.
addition,
original-site
obtained
by
alternating
ligand,
wherein
formation
rationalized
radical
chain
process.
