Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 13, 2024
Ni-catalyzed
multicomponent
cross-couplings
have
emerged
as
a
powerful
strategy
for
efficiently
constructing
complex
molecular
architectures
from
diverse
array
of
organic
halides.
Despite
its
potential,
selectively
forming
multiple
chemical
bonds
in
single
operation,
particularly
the
realm
cross-electrophile
coupling
catalysis,
remains
significant
challenge.
In
this
study,
we
developed
consecutive
open-shell
reductive
Ni
enabling
formation
two
geminal
C(sp
Organic Process Research & Development,
Journal Year:
2024,
Volume and Issue:
28(2), P. 338 - 366
Published: Jan. 18, 2024
This
review
summarizes
examples
of
organic
electrosynthesis
from
the
peer-reviewed
literature
2000
to
2023
that
have
been
conducted
on
scales
20
g
or
above.
A
significant
portion
these
were
a
≤100
scale,
while
detailed
reports
kilogram-scale
remain
scarce
in
pharmaceutical
industry.
In
addition
chemical
transformation,
this
also
highlights
type
reactor
used
and
projected
productivity
metric
as
ways
compare
different
reports.
The
selected
scale-ups
described
herein
illustrate
remaining
challenges
currently
preventing
routine
use
large-scale
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.
Organic Process Research & Development,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 7, 2025
A
scalable
electrochemical
process
to
synthesize
iminophosphorane
ligands
is
reported.
The
application
of
these
iminophosphoranes
was
recently
reported
in
Ni-catalyzed
cross-electrophile
and
C–N
cross-couplings.
use
parallel
plate
flow
reactors
enables
the
synthesis
on
a
multigram
scale,
with
selected
examples
up
0.6
kg
scale.
Direct
crystallization
from
end
reaction
mixture
for
provides
facile
isolation
processes.
This
article
also
details
improvements
our
capabilities
across
scales,
including
addressing
material
compatibility
issues,
increasing
accessible
range
rates,
integration
analytical
technology
tools.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 26, 2024
Cross-electrophile
coupling
(XEC),
defined
by
us
as
the
cross-coupling
of
two
different
σ-electrophiles
that
is
driven
catalyst
reduction,
has
seen
rapid
progression
in
recent
years.
As
such,
this
review
aims
to
summarize
field
from
its
beginnings
up
until
mid-2023
and
provide
comprehensive
coverage
on
synthetic
methods
current
state
mechanistic
understanding.
Chapters
are
split
type
bond
formed,
which
include
C(sp
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
unknown, P. 3184 - 3190
Published: Feb. 6, 2025
A
direct
electroreductive
functionalization
of
tropones
employing
aldehydes
as
alkylating
agents
is
reported.
This
C(sp2)-H
process
leverages
the
mediation
electroactive
nickel
complexes,
enabling
a
wide
range
both
native
and
substituted
(44
examples)
to
be
alkylated
selectively
at
α-position
in
high
yields
(up
90%).
Combined
electrochemical,
spectroelectrochemical,
computational
analyses
disclosed
whole
mechanistic
pathway
revealed
key
role
played
by
reduced
Ni
complexes
activating
tropone
core
toward
condensation
with
aldehydes.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(24), P. 16753 - 16763
Published: June 11, 2024
In
the
realm
of
organic
synthesis,
catalytic
and
stereoselective
formation
C-glycosidic
bonds
is
a
pivotal
process,
bridging
carbohydrates
with
aglycones.
However,
inherent
chirality
saccharide
scaffold
often
has
substantial
impact
on
stereoinduction
imposed
by
chiral
ligand.
this
study,
we
have
established
an
unprecedented
zirconaaziridine-mediated
asymmetric
nickel
catalysis,
enabling
diastereoselective
coupling
bench-stable
glycosyl
phosphates
range
(hetero)aromatic
glycal
iodides
as
feasible
electrophiles.
Our
developed
method
showcases
broad
scope
high
tolerance
for
various
functional
groups.
More
importantly,
precise
stereocontrol
toward
both
anomeric
configurations
forming
C(sp2)-glycosides
can
be
realized
simply
utilizing
popular
bioxazoline
(biOx)
ligands
in
reductive
Ni
catalysis.
Regarding
operating
mechanism,
experimental
computational
studies
support
occurrence
redox
transmetalation
leading
to
transient,
bimetallic
Ni–Zr
species
that
acts
potent
efficient
single-electron
reductant
process.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(24)
Published: April 12, 2024
Abstract
Nickel‐catalyzed
cross‐electrophile
coupling
reactions
of
two
aliphatic
alcohol
derivatives
remain
a
challenge.
Herein,
we
report
nickel‐catalyzed
reductive
methylation
reaction
mesylates
with
methyl
tosylate.
This
provides
straightforward
access
to
compounds
bearing
groups
from
alkyl
derivatives.
Isotopically
labelled
substrates
and
reagents
can
be
employed
in
the
provide
perdeuterated
13
C‐labelled
products.
transformation
achieved
by
employing
stoichiometric
Mn
reductant
or
electrochemically.
Additionally,
mechanistic
experiments
show
that
iodides
are
key
intermediates
which
undergo
stereoablative
via
radical
intermediates.
Chemistry - An Asian Journal,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 12, 2025
Abstract
This
review
discloses
nickel‐
and
cobalt‐catalyzed
coupling
reactions
that
allow
C−P
bond
formation.
Activation
of
C−halide
bonds
to
form
phosphonium,
pentavalent
phosphorus,
or
trivalent
phosphorous
compounds
has
been
reported
with
both
metals.
However,
the
conversion
C−O
((activated)
ethers,
carbonates,
acetates)
into
ones
only
described
Ni.
Similarly,
there
are
more
examples
C−Y
(Y=C,
S,
N,
B)
activations
catalyzed
by
Ni
than
Co.
Nevertheless,
cross‐dehydrogenative
reaction
between
a
P−H
reagent
C−H
often
cobalt
nickel.
In
addition,
for
metals,
electrolytic
photocatalytic
processes
have
shown
produce
variety
containing
molecules.
aims
provide
an
overview
potential
metals
formation
highlight
remaining
challenges.
