Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Jan. 28, 2025
Abstract
Motivated
by
the
inherent
benefits
of
synergistically
combining
electrochemical
methodologies
with
nickel
catalysis,
we
present
here
a
Ni-catalyzed
enantioselective
electroreductive
cross-coupling
benzyl
chlorides
aryl
halides,
yielding
chiral
1,1-diaryl
compounds
good
to
excellent
enantioselectivity.
This
catalytic
reaction
can
not
only
be
applied
chlorides/bromides,
which
are
challenging
access
other
means,
but
also
containing
silicon
groups.
Additionally,
absence
sacrificial
anode
lays
foundation
for
scalability.
The
combination
cyclic
voltammetry
analysis
electrode
potential
studies
suggests
that
Ni
I
species
activate
halides
via
oxidative
addition
and
alkyl
single
electron
transfer.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
53(2), P. 566 - 585
Published: Dec. 5, 2023
This
tutorial
review
explains
the
use
of
cyclic
voltammetry
and
chronoamperometry
to
interrogate
reaction
mechanisms,
optimize
electrochemical
reactions,
or
design
new
reactions.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(21), P. 11518 - 11523
Published: May 16, 2023
The
first
examples
of
enantioselective
doubly
decarboxylative
cross
coupling
are
disclosed.
Malonate
half
amides
smoothly
coupled
to
a
variety
primary
carboxylic
acids
after
formation
the
corresponding
redox-active
esters
under
Ni-electrocatalytic
conditions
using
new
chiral
ligand
based
on
PyBox,
resulting
in
with
α-alkylated
stereocenters.
scope
reaction
is
broad,
tolerating
numerous
functional
groups,
and
uniformly
proceeds
high
ee.
Finally,
potential
utility
this
radical–radical
reductive
simplify
synthesis
demonstrated
case
studies.
Accounts of Chemical Research,
Journal Year:
2024,
Volume and Issue:
57(5), P. 751 - 762
Published: Feb. 12, 2024
ConspectusAfter
decades
of
palladium
dominating
the
realm
transition-metal-catalyzed
cross-coupling,
recent
years
have
witnessed
exciting
advances
in
development
new
nickel-catalyzed
cross-coupling
reactions
to
form
C(sp3)
centers.
Nickel
possesses
distinct
properties
compared
with
palladium,
such
as
facile
single-electron
transfer
electrophiles
and
rapid
C–C
reductive
elimination
from
NiIII.
These
properties,
among
others,
make
nickel
particularly
well-suited
for
(RCC)
which
two
are
coupled
an
exogenous
reductant
is
used
turn
over
metal
catalyst.
Ni-catalyzed
RCCs
use
readily
available
stable
starting
materials
exhibit
good
functional
group
tolerance,
makes
them
appealing
applications
synthesis
complex
molecules.
Building
upon
foundational
work
by
groups
Kumada,
Durandetti,
Weix,
well
advancements
enantioselective
redox-neutral
cross-couplings
led
Fu
co-workers,
we
initiated
a
program
explore
feasibility
developing
highly
RCCs.
Our
research
has
also
been
driven
keen
interest
unraveling
factors
contributing
enantioinduction
electrophile
activation
seek
avenues
advancing
our
understanding
further
these
reactions.In
first
part
this
Account,
organize
reported
methods
on
basis
identity
electrophiles,
including
benzylic
chlorides,
N-hydroxyphthalimide
(NHP)
esters,
α-chloro
esters
nitriles.
We
highlight
how
selection
specific
chiral
ligands
plays
pivotal
role
achieving
high
cross-selectivity
enantioselectivity.
In
addition,
show
that
reduction
can
be
accomplished
not
only
heterogeneous
reductants,
Mn0,
but
soluble
organic
tetrakis(dimethylamino)ethylene
(TDAE),
electrochemically.
The
homogeneous
TDAE,
suited
studying
mechanism
transformation.
Although
Account
primarily
focuses
RCCs,
using
trifluoroborate
(BF3K)
salts
radical
precursors
dual-Ni/photoredox
systems.At
end
summarize
relevant
mechanistic
studies
closely
related
asymmetric
alkenylation
developed
laboratory
provide
context
between
others.
discuss
ligand
influence
rates
mechanisms
mode
generation
optimize
yield
RCC.
endeavors
offer
insights
intricate
at
play
goal
rate
improve
substrate
scope
anticipate
share
guidance
field.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(11), P. 9055 - 9076
Published: May 29, 2024
Metallaphotoredox
catalysis
can
unlock
useful
pathways
for
transforming
organic
reactants
into
desirable
products,
largely
due
to
the
conversion
of
photon
energy
chemical
potential
drive
redox
and
bond
transformation
processes.
Despite
importance
these
processes
cross-coupling
reactions
other
transformations,
their
mechanistic
details
are
only
superficially
understood.
In
this
review,
we
have
provided
a
detailed
summary
various
photoredox
mechanisms
that
been
proposed
date
Ni-bipyridine
(bpy)
complexes,
focusing
separately
on
photosensitized
direct
excitation
reaction
By
highlighting
multiple
key
findings,
depict
how
mechanisms,
which
ultimately
define
substrate
scope,
themselves
defined
by
ground-
excited-state
geometric
electronic
structures
Ni-based
intermediates.
We
further
identify
knowledge
gaps
motivate
future
studies
development
synergistic
research
approaches
spanning
physical,
organic,
inorganic
chemistry
communities.
Nature Catalysis,
Journal Year:
2024,
Volume and Issue:
7(6), P. 733 - 741
Published: May 7, 2024
Abstract
Nickel
photoredox
catalysis
has
resulted
in
a
rich
development
of
transition-metal-catalysed
transformations
for
carbon–heteroatom
bond
formation.
By
harnessing
light
energy,
the
transition
metal
can
attain
oxidation
states
that
are
difficult
to
achieve
through
thermal
chemistry
catalytic
manifold.
For
example,
nickel
reactions
have
been
reported
both
synthesis
anilines
and
aryl
ethers
from
aryl(pseudo)halides.
However,
oxidative
addition
simple
systems
is
often
sluggish
absence
special,
electron-rich
ligands,
leading
catalyst
decomposition.
Electron-rich
electrophiles
therefore
currently
fall
outside
scope
many
field.
Here
we
provide
conceptual
solution
this
problem
demonstrate
nickel-catalysed
C–heteroatom
bond-forming
arylthianthrenium
salts,
including
amination,
oxygenation,
sulfuration
halogenation.
Because
redox
properties
salts
primarily
dictated
by
thianthrenium,
highly
donors
be
unlocked
using
NiCl
2
under
irradiation
form
desired
C‒heteroatom
bonds.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(5), P. 3043 - 3051
Published: Jan. 26, 2024
Cross-electrophile
coupling
has
emerged
as
an
attractive
and
efficient
method
for
the
synthesis
of
C(sp2)–C(sp3)
bonds.
These
reactions
are
most
often
catalyzed
by
nickel
complexes
nitrogenous
ligands,
especially
2,2′-bipyridines.
Precise
prediction,
selection,
design
optimal
ligands
remains
challenging,
despite
significant
increases
in
reaction
scope
mechanistic
understanding.
Molecular
parameterization
statistical
modeling
provide
a
path
to
development
improved
bipyridine
that
will
enhance
selectivity
existing
broaden
electrophiles
can
be
coupled.
Herein,
we
describe
generation
computational
ligand
library,
correlation
observed
outcomes
with
features
silico
Ni-catalyzed
cross-electrophile
coupling.
The
new
nitrogen-substituted
display
5-fold
increase
product
formation
versus
homodimerization
when
compared
current
state
art.
This
yield
was
general
several
couplings,
including
challenging
aryl
chloride
N-alkylpyridinium
salt.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 14, 2025
Ni-catalyzed
asymmetric
reductive
cross-coupling
reactions
provide
rapid
and
modular
access
to
enantioenriched
building
blocks
from
simple
electrophile
precursors.
Reductive
coupling
that
can
diverge
through
a
common
organometallic
intermediate
two
distinct
families
of
products
are
particularly
versatile
but
underdeveloped.
Here,
we
describe
the
development
bis(oxazoline)
ligand
enables
desymmetrization
meso-anhydrides.
When
secondary
benzylic
electrophiles
employed,
doubly
stereoselective
acyl
proceeds
give
ketone
with
catalyst
control
over
three
newly
formed
stereogenic
centers.
Alternatively,
use
primary
alkyl
halides
in
presence
an
additional
halogen
atom
transfer
results
decarbonylative
alkylation
β-alkyl
acids.
Analysis
reaction
rates
for
range
both
catalysts
substrates
supports
notion
tuning
different
activation
steps
is
required
enhanced
performance.
These
studies
illustrate
how
design
Ni-acyl
either
or
highlight
dual
systems
be
used
engage
unactivated
coupling.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 10, 2025
Despite
the
progress
made
in
field
of
synthetic
organic
photocatalysis
over
past
decade,
use
higher
wavelengths,
especially
those
deep-red
portion
electromagnetic
spectrum,
remains
comparatively
rare.
We
have
previously
disclosed
that
a
well-defined
N,C,N-pincer
bismuthinidene
(1a)
can
undergo
formal
oxidative
addition
into
wide
range
aryl
electrophiles
upon
absorption
low-energy
red
light.
In
this
study,
we
map
out
photophysical
dynamics
1a
and
glean
insights
nature
excited
state
responsible
for
activation
electrophiles.
Transient
emission
techniques
reveal
that,
irradiation
with
light,
complex
undergoes
direct
S0
→
S1
metal-to-ligand
charge
transfer
(MLCT)
transition,
followed
by
rapid
intersystem
crossing
(ISC)
to
highly
reducing
emissive
triplet
(−2.61
V
vs
Fc+/0
MeCN).
The
low
dissipative
losses
incurred
during
ISC
(∼6%
incident
light
energy)
help
rationalize
ability
convert
useful
chemical
energy.
Spectroelectrochemical
computational
data
support
charge-separated
excited-state
structure
radical-anion
character
on
ligand
radical-cation
bismuth.
Kinetic
studies
competition
experiments
afford
mechanism
iodides;
concerted
inner-sphere
processes
from
are
ruled
out,
strongly
supporting
pathway
proceeds
via
outer-sphere
dissociative
electron
transfer.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(44), P. 23910 - 23917
Published: Oct. 26, 2023
The
merger
of
electrochemistry
and
transition
metal
catalysis
has
emerged
as
a
powerful
tool
to
join
two
electrophiles
in
an
enantioselective
manner.
However,
the
development
electroreductive
cross-couplings
olefins
remains
challenge.
Inspired
by
advantages
synergistic
use
with
nickel
catalysis,
we
present
here
Ni-catalyzed
cross-coupling
acrylates
aryl
halides
alkyl
bromides,
which
affords
chiral
α-aryl
carbonyls
good
excellent
enantioselectivity.
Additionally,
this
catalytic
reaction
can
be
applied
(hetero)aryl
chlorides,
is
difficult
achieve
other
methods.
combination
cyclic
voltammetry
analysis
electrode
potential
studies
suggests
that
NiI
species
activates
oxidative
addition
bromides
single-electron
transfer.
Accounts of Chemical Research,
Journal Year:
2023,
Volume and Issue:
56(20), P. 2851 - 2865
Published: Sept. 29, 2023
ConspectusTransition-metal
catalyzed
cross-coupling
reactions
are
fundamental
in
organic
chemistry,
facilitating
strategic
bond
formations
for
accessing
natural
products,
materials,
agrochemicals,
and
pharmaceuticals.
Redox
chemistry
enables
access
to
elusive
mechanisms
through
single-electron
processes
as
an
alternative
classical
two-electron
strategies
predominated
by
palladium
catalysis.
The
seminal
reports
of
Baran,
MacMillan,
Doyle,
Molander,
Weix,
Lin,
Fu,
Reisman,
others
merging
redox
perturbation
(photochemical,
electrochemical,
purely
chemical)
with
catalysis
pivotal
the
current
resurgence
mechanistic
understanding
first-row
transition
metal-based
hallmark
this
platform
is
systematic
modulation
transition-metal
oxidation
states
a
photoredox
catalyst
or
at
heterogeneous
electrode
surface.
Electrocatalysis
photocatalysis
enhance
metal
catalysis'
capacity
formation
electron-
energy-transfer
that
promote
otherwise
challenging
elementary
steps
mechanisms.
Cross-coupling
conditions
promoted
electrocatalysis
mild,
proceeds
exceptionally
high
chemoselectivity
wide
functional
group
tolerance.
interfacing
abundant
has
brought
about
paradigm
shift
technology
practitioners
quickly
applying
these
tools
synthesizing
fine
chemicals
pharmaceutically
relevant
motifs.
In
particular,
merger
Ni
electro-
photochemistry
ushered
new
era
carbon-carbon
carbon-heteroatom
cross-couplings
expanded
generality
compared
their
thermally
driven
counterparts.
Over
past
decade,
we
have
developed
enabling
photo-
electrochemical
methods
throughout
our
combined
research
experience
industry
(BMS,
AstraZeneca)
academia
(Professor
Scripps
Research)
cross-disciplinary
collaborative
environments.
Account,
will
outline
recent
progress
from
present
laboratories
electrochemically
mediated
Ni-catalyzed
cross-couplings.
By
highlighting
methodologies,
also
compare
features
both
photochemical
forging
C(sp2)-C(sp3),
C(sp3)-C(sp3),
C-O,
C-N,
C-S
bonds.
Through
side-by-side
comparisons,
hope
demystify
subtle
differences
between
two
complementary
enact
control
over
Finally,
building
off
collective
ourselves
rest
community,
propose
tactical
user
guide
aid
practitioner
rapidly
such
synthetic
designs.