Research Square (Research Square),
Journal Year:
2022,
Volume and Issue:
unknown
Published: March 23, 2022
Abstract
The
development
of
transition
metal-catalyzed
β
-C−H
bond
activation
via
highly-strained
4-membered
metallacycles
has
been
a
formidable
task.
So
far,
only
scarce
examples
have
reported
to
undergo
metallacycles,
and
all
them
rely
on
precious
metals.
In
contrast,
earth-abundant
inexpensive
3d
still
remains
an
elusive
challenge.
Herein,
we
report
phosphine
oxide-ligated
Ni−Al
bimetallic
catalyst
activate
secondary
benzylic
C(sp
3
)−H
bonds
formamides
nickelacycles,
providing
series
α,β
-unsaturated
γ
-lactams
in
up
97%
yield.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(41), P. 18810 - 18816
Published: Oct. 7, 2022
A
chiral
phosphine
oxide-ligated
Ni–Al
bimetallic
catalyst
was
used
to
realize
an
enantioselective
C2–H
alkylation
of
pyridines
without
the
need
a
C2-block.
wide
range
pyridines,
including
unsubstituted
pyridine,
C3,
C4,
and
C2-substituted
even
complex
pyridine-containing
bioactive
molecules
are
well
compatible
with
reaction,
providing
up
81%
yield
97%
ee.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(19), P. 11716 - 11733
Published: Sept. 12, 2022
C–H
functionalization
via
hydrogen
atom
transfer
is
an
attractive
method
of
decorating
inert
bonds,
yet
it
remains
challenging
so
far.
In
such
a
reaction,
the
abstractor
generally
plays
crucial
role
in
determining
reactivity
and
selectivity.
Among
various
abstractors
developed,
N-hydroxyphthalimide
(NHPI)
bearing
N-hydroxy
group
two
adjacent
carbonyl
groups
has
features
including
easy
preparation,
convenient
modification,
superior
catalytic
ability
many
reactions.
A
large
variety
electron-deficient
catalysts
based
on
NHPI,
NHPI
derivatives
analogues,
have
been
successively
developed
applied
broad
range
This
review
comprehensively
summarizes
development
catalysts,
with
special
focus
relationship
between
structure
performance.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: May 26, 2022
Hydroarylation
of
alkynes
with
unactivated
C(sp2)-H
bonds
via
chelated
C-H
metalation
mainly
occurs
at
γ-position
to
the
coordinating
atom
directing
groups
stable
5-membered
metallacycles,
while
β-C(sp2)-H
bond-involved
hydroarylation
has
been
a
formidable
challenge.
Herein,
we
used
phosphine
oxide-ligated
Ni-Al
bimetallic
catalyst
enable
β-C-H
hydroarylations
rare
7-membered
nickelacycle.
Chemical Communications,
Journal Year:
2022,
Volume and Issue:
58(88), P. 12260 - 12273
Published: Jan. 1, 2022
Compared
with
non-ligated
Ni-Al
bimetallic
catalysis,
bifunctional
ligand-ligated
catalysis
displays
stronger
synergism,
not
only
affecting
the
electronic
properties
and
steric
hindrance
of
substrates,
but
also
producing
a
directing
effect
for
facile
control
reactivity,
site
selectivity
enantioselectivity
in
activation
C-H
C-C
bonds.
This
review
will
give
brief
summary
research
advances
this
field,
highlighting
development
ligands
their
applications.
ACS Omega,
Journal Year:
2022,
Volume and Issue:
7(8), P. 6439 - 6448
Published: Feb. 14, 2022
The
direct
metal-catalyzed
C–H
functionalization
of
arenes
has
emerged
as
a
powerful
tool
for
streamlining
the
synthesis
complex
molecular
scaffolds.
However,
despite
different
chemical
environments,
energy
values
all
bonds
are
within
fairly
narrow
range;
hence,
regioselective
bond
poses
great
challenge.
use
covalently
bound
directing
groups
is
to
date
most
exploited
approach
achieve
arenes.
required
installation
and
removal
those
serious
drawback.
Recently,
new
strategies
distal
based
on
noncovalent
forces
(hydrogen
bonds,
Lewis
acid–base
interactions,
ionic
or
electrostatic
forces,
etc.)
have
been
developed
tackle
these
issues.
Nowadays,
approaches
already
showcased
impressive
advances.
Therefore,
aim
this
mini-review
cover
chronologically
how
groundbreaking
evolved
over
past
decade.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(42)
Published: Aug. 29, 2022
Enantioselective
Ni-catalyzed
C(sp3
)-H
bond
activation
remains
an
elusive
challenge.
Herein,
we
used
phosphine
oxide-ligated
Ni-Al
bimetallic
catalyst
to
realize
enantioselective
aliphatic
of
formamides,
providing
a
series
chiral
N-containing
heterocycles
in
40-95
%
yield
and
70-95
ee.
Synthesis,
Journal Year:
2022,
Volume and Issue:
54(21), P. 4773 - 4783
Published: March 17, 2022
Abstract
Co-catalyzed
C–H
functionalization
has
received
great
attention
due
to
the
high
earth
abundance,
low
biotoxicity,
and
unique
reactivity
of
cobalt;
enantioselective
control
these
reactions
been
a
formidable
challenge.
Various
efficient
strategies
have
recently
developed
for
functionalization,
but
there
is
no
topical
review
this
field.
Herein,
we
give
detailed
summary
rapidly
growing
field,
highlighting
critical
progress,
current
challenges,
future
trends.
1
Introduction
2
Enantioselective
Functionalization
via
Low-Valent
Co
Catalysis
2.1
Chiral
Diphosphines
Control
2.2
Monophosphines
or
N-Heterocyclic
Carbenes
3
High-Valent
3.1
Acids
3.2
Cp
Ligands
4
Conclusions
Outlook
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Aug. 22, 2024
Herein,
we
describe
an
innovative
approach
to
the
asymmetric
electrochemical
α-alkylation
of
aldehydes
facilitated
by
a
newly
designed
bifunctional
chiral
electrocatalyst.
The
highly
efficient
electrocatalyst
combines
aminocatalyst
with
redox
mediator.
It
plays
dual
role
as
mediator
for
electrooxidation,
while
simultaneously
providing
remarkable
induction
stereoselective
aldehydes.
Additionally,
this
novel
catalyst
exhibits
enhanced
catalytic
activity
and
excellent
control
comparable
conventional
systems.
As
result,
strategy
provides
new
avenue
versatile
electrochemistry.
electrooxidation
diverse
phenols
enables
C-H/C-H
oxidative
in
chemo-
fashion.
Detailed
mechanistic
studies
experiments
cyclic
voltammetry
analysis
demonstrate
possible
reaction
pathways
origin
enantio-induction.
