Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: Feb. 7, 2025
Multi-component
multi-functionalization
reactions
involving
active
intermediates
are
powerful
tools
for
rapidly
generating
a
wide
array
of
compounds.
Metal
carbynoids,
with
their
distinct
reactivity,
hold
great
promise
developing
synthetic
methodologies.
However,
application
in
catalytic
transfer
has
been
hindered
by
the
limited
availability
suitable
precursors.
In
this
study,
we
investigate
potential
α-halo
Rh-carbenes,
leveraging
concept
metal
carbynoids
reactions.
Through
chiral
phosphoric
acid-catalyzed
asymmetric
trifunctionalization,
have
developed
method
synthesizing
variety
α-cyclic
ketal
β-amino
esters
high
yields
and
excellent
enantioselectivity.
Our
extensive
experimental
computational
studies
reveal
that
Rh-carbenes
exhibit
carbynoid
properties,
which
facilitate
transformation
into
functionalized
Fischer-type
through
decomposition
C-halo
bond.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(19), P. 10836 - 10856
Published: Jan. 1, 2021
The
catalytic
dicarbofunctionalization
of
unsaturated
π
bonds
represents
a
powerful
platform
for
the
rapid
construction
complex
motifs.
Despite
remarkable
progress,
novel
and
efficient
methods
achieving
such
transformations
under
milder
conditions
with
chemo-,
regio-,
stereoselectivity
still
remain
significant
challenge;
thus,
their
development
is
highly
desirable.
Recently,
merging
nickel
catalysis
radical
chemistry
offers
new
benign
unprecedented
reactivity
selectivity.
In
this
review,
we
summarize
recent
advances
in
area
by
underpinning
domino
involving
capture
to
provide
clear
overview
reaction
designs
mechanistic
scenarios.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(2), P. 1180 - 1200
Published: Jan. 5, 2022
Key
similarities
and
differences
of
Pd
Ni
in
catalytic
systems
are
discussed.
Overall,
catalyze
a
vast
number
similar
C–C
C–heteroatom
bond-forming
reactions.
However,
the
smaller
atomic
radius
lower
electronegativity
Ni,
as
well
more
negative
redox
potentials
low-valent
species,
often
provide
higher
reactivity
oxidative
addition
or
insertion
reactions
persistence
alkyl-Ni
intermediates
against
β-hydrogen
elimination,
thus
enabling
activation
reluctant
electrophiles,
including
alkyl
electrophiles.
Another
key
point
relates
to
stability
open-shell
electronic
configurations
Ni(I)
Ni(III)
compared
with
Pd(I)
Pd(III).
Nickel
very
involve
interconvertible
Ni(n+)
active
species
variable
oxidation
states
(Ni(0),
Ni(I),
Ni(II),
Ni(III)).
In
contrast,
involving
Pd(III)
still
relatively
less
developed
may
require
facilitation
by
special
ligands
merging
photo-
electrocatalysis.
high
Pd(n+)
ensure
their
facile
reduction
Pd(0)
under
assistance
numerous
reagents
solvents,
providing
concentrations
molecular
Pd1(0)
complexes
that
can
reversibly
aggregate
into
Pdn
clusters
nanoparticles
form
cocktail
Pdn(0)
various
nuclearities
(i.e.,
values
"n").
Ni(0)
strong
reductants;
they
sensitive
deactivation
air
other
oxidizers
and,
consequence,
operate
at
catalyst
loadings
than
palladium
same
The
ease
robustness
versatility
for
catalysis,
whereas
variety
enables
diverse
uncommon
reactivity,
albeit
requiring
efforts
stabilization
nickel
systems.
As
discussion,
we
note
easily
"cocktail
particles"
different
but
(Pd1,
Pdn,
NPs),
behave
species"
is
stable
nuclearities.
Undoubtedly,
there
stronger
demand
ever
not
only
develop
improved
efficient
catalysts
also
understand
mechanisms
Science,
Journal Year:
2022,
Volume and Issue:
376(6591), P. 410 - 416
Published: April 21, 2022
Cross-electrophile
coupling
(XEC)
reactions
of
aryl
and
alkyl
electrophiles
are
appealing
but
limited
to
specific
substrate
classes.
Here,
we
report
electroreductive
XEC
previously
incompatible
including
tertiary
bromides,
chlorides,
aryl/vinyl
triflates.
Reactions
rely
on
the
merger
an
electrochemically
active
complex
that
selectively
reacts
with
bromides
through
1e
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(16), P. 7015 - 7029
Published: April 12, 2022
Compounds
rich
in
sp3-hybridized
carbons
are
desirable
drug
discovery.
Nickel-catalyzed
hydrocarbonation
of
alkenes
is
a
potentially
efficient
method
to
synthesize
these
compounds.
By
using
abundant,
readily
available,
and
stable
as
pro-nucleophiles,
reactions
can
have
broad
scope
high
functional
group
tolerance.
However,
this
methodology
still
an
early
stage
development,
the
first
examples
were
reported
only
2016.
Herein,
we
summarize
progress
emerging
field,
with
emphasis
on
enantioselective
reactions.
We
highlight
major
developments,
critically
discuss
wide
range
possible
mechanisms,
offer
our
perspective
state
challenges
field.
hope
Perspective
will
stimulate
future
works
area,
making
widely
applicable
organic
synthesis.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: May 23, 2022
The
carbene
and
photocatalyst
co-catalyzed
radical
coupling
of
acyl
electrophile
a
precursor
is
emerging
as
attractive
method
for
ketone
synthesis.
However,
previous
reports
mainly
limited
to
prefunctionalized
precursors
two-component
coupling.
Herein,
an
N-heterocyclic
catalyzed
decarboxylative
carboxylic
acids
imidazoles
disclosed,
in
which
the
are
directly
used
precursors.
could
also
be
generated
situ
by
reaction
acid
with
CDI
thus
furnishing
formally
two
acids.
In
addition,
successfully
extended
three-component
using
alkene
third
partner
via
relay
process.
mild
conditions,
operational
simplicity,
use
reacting
partners
make
our
powerful
strategy
construction
complex
ketones
from
readily
available
starting
materials,
late-stage
modification
natural
products
medicines.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(46), P. 21278 - 21286
Published: Nov. 14, 2022
Cross-coupling
platforms
are
traditionally
built
around
a
sequence
of
closed-shell
steps,
such
as
oxidative
addition,
transmetalation,
and
reductive
elimination.
Herein,
we
describe
dual
photo/nickel
catalytic
manifold
that
performs
cross-coupling
via
complementary
involving
free
radical
generation,
sorting
selective
binding
to
Ni(II)
center,
bimolecular
homolytic
substitution
(SH2)
at
high-valent
nickel-alkyl
complex.
This
enables
the
hitherto
elusive
diverse
aliphatic
carboxylic
acids
generate
valuable
C(sp3)-C(sp3)-products.
Notably,
powerful
SH2
mechanism
provides
general
access
sterically
encumbered
quaternary
carbon
centers,
addressing
long-standing
challenge
in
fragment
coupling
chemistry.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(9), P. 3989 - 3997
Published: Feb. 22, 2022
Chiral
phosphine-containing
skeletons
are
important
motifs
in
bioactive
natural
products,
pharmaceuticals,
chiral
catalysts,
and
ligands.
Herein,
we
report
a
general
modular
platform
to
access
α-aryl
phosphorus
compounds
via
Ni/photoredox-catalyzed
enantioconvergent
reductive
cross-coupling
between
α-bromophosphates
aryl
iodides.
This
dual
catalytic
regime
exhibited
high
efficiency
good
functional
group
compacity.
A
wide
variety
of
substrates
bearing
diverse
set
groups
could
be
converted
into
phosphates
excellent
yields
enantioselectivities.
The
utility
the
method
was
also
demonstrated
by
development
new
phosphine
ligand
synthesis
enzyme
inhibitor
derivatives.
detailed
mechanistic
studies
supported
radical
chain
process
revealed
unique
distinction
compared
with
traditional
cross-coupling.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(18), P. 12300 - 12309
Published: April 24, 2024
Metallaphotoredox
cross-coupling
is
a
well-established
strategy
for
generating
clinically
privileged
aliphatic
scaffolds
via
single-electron
reactivity.
Correspondingly,
expanding
metallaphotoredox
to
encompass
new
C(
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 16, 2025
Quaternary
carbon
centers
are
widespread
structural
motifs,
thus
representing
extensive
interest
in
organic
synthesis.
We
describe
here
an
efficient
nickel-catalyzed
intermolecular,
Markovnikov-selective
arylation
of
minimally
functionalized
alkenes
with
stable
organoborons,
affording
a
broad
range
cyclic
or
acyclic
quaternary
under
mild
conditions.
The
utilization
the
diimine
ligand
is
critical
for
high
reactivity
and
chemoselectivity.
Furthermore,
using
bulky
chiral
as
Ni
catalyst,
stereocenters
can
be
readily
prepared
levels
enantiocontrol.
Mechanism
studies
suggest
that,
before
protonation,
rare
nickel
shift
from
alkyl
to
aryl
might
occur.