In
the
realm
of
biaryl
synthesis,
Ullmann
homocoupling
reaction
is
a
fundamental
process
for
constructing
compounds
and
has
historically
been
driven
by
copper
catalysis.
However,
significant
studies
have
made
in
Ullmann-type
coupling
reactions,
particularly
formation
structures,
leading
to
more
sustainable
efficient
synthetic
pathways.
Recent
research
concentrated
on
devising
innovative
catalytic
systems,
including
palladium,
gold,
nickel
nanoparticles,
bimetallic
species,
surmount
limitations
conventional
catalysts.
These
advancements
broadened
range
substrates
enhanced
efficiency
under
gentler
conditions,
line
with
principles
green
chemistry.
Mechanistic
instrumental
these
developments,
focusing
nonchain
single-electron
transfer
(SET)
mechanism.
Additionally,
use
recyclable
heterogeneous
catalysts
mitigated
stringent
conditions
associated
original
reaction.
As
continues
evolve,
asymmetric
anticipated
become
key
tool
synthesis
complex
natural
products
heterocyclic
systems
pertinent
medicinal
This
review
aims
cover
recent
developments
compounds.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(11)
Published: Jan. 19, 2022
We
have
developed
a
nickel-catalyzed
desymmetric
reductive
cyclization/coupling
of
1,6-dienes.
The
reaction
provides
an
efficient
method
for
constructing
chiral
tertiary
alcohol
and
quaternary
stereocenter
by
single
operation.
has
excellent
diastereoselectivity
high
enantioselectivity,
broad
substrate
scope,
as
well
good
tolerance
functional
groups.
Preliminary
mechanism
studies
show
that
alkyl
nickel(I)
species
are
involved
in
the
reaction.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(47)
Published: Oct. 5, 2022
The
first
nickel-catalyzed
highly
enantioselective
reductive
Ullmann
coupling
of
ortho-chlorinated
aryl
aldehyde
was
achieved
under
mild
reaction
conditions
with
a
chiral
2,2'-bipyridine
ligand
(+)-DTB-SBpy,
thus
providing
axially
biphenyl
or
binaphthyl
dials
up
to
99
%
yield
and
99.5:0.5
er.
versatility
the
products
as
common
synthetic
intermediates
for
diverse
ligands,
catalysts,
functional
molecules
demonstrated
by
short-step
transformations.
This
protocol
also
allowed
concise
formal
total
synthesis
biologically
active
natural
(+)-kotanin,
(-)-isoschizandrin
(+)-gossypol.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: Oct. 19, 2022
The
utilization
of
readily
available
and
non-toxic
water
by
photocatalytic
splitting
is
highly
attractive
in
green
chemistry.
Herein
we
report
that
light-induced
oxidative
half-reaction
effectively
coupled
with
reduction
organic
compounds,
which
provides
a
avenue
to
use
as
an
electron
donor
enable
reductive
transformations
substances.
present
strategy
allows
various
aryl
bromides
undergo
smoothly
the
coupling
Pd/g-C3N4*
photocatalyst,
giving
pollutive
reductant-free
method
for
synthesizing
biaryl
skeletons.
Moreover,
visible-light
energy
endows
this
process
more
advantages
including
mild
conditions
good
functional
group
tolerance.
Although
has
some
disadvantages
such
environmentally
unfriendly
1,2-dioxane,
addition
Na2CO3
so
on,
it
can
guide
chemists
reducing
agent
develop
clean
procedures
reactions.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(10), P. 6795 - 6803
Published: May 3, 2023
Herein,
we
report
a
nickel-catalyzed
asymmetric
three-component
trans-dicarbofunctionalization
of
β-substituted
α-naphthyl
propargylic
alcohols
using
readily
available
aryl
and
benzyl
halides
as
the
coupling
partners
under
reductive
conditions.
This
cross-electrophile
strategy
enables
synthesis
various
axially
chiral
allylic
bearing
tetrasubstituted
olefinic
unit
in
complete
regio-
E
selectivity,
well
high
enantiocontrol.
Relying
on
hydroxyl
group
functional
handle,
such
structural
motifs
are
successfully
derivatized
into
diverse
functional-group-rich
alkenes.
Accounts of Chemical Research,
Journal Year:
2024,
Volume and Issue:
57(6), P. 957 - 970
Published: March 6, 2024
ConspectusThe
innovation
of
chiral
ligands
has
been
crucial
for
the
asymmetric
synthesis
functional
molecules,
as
demonstrated
by
several
types
widely
applied
"privileged"
ligands.
In
this
context,
pyridine-derived
ligands,
far
some
oldest
and
most
utilized
in
catalysis,
have
attracted
considerable
research
interest
past
half-century.
However,
development
broadly
applicable
pyridine
units
(CPUs)
plagued
intertwining
challenges,
thus
delaying
advancements
many
reactions.This
Account
aims
to
summarize
recent
progress
new
CPU-containing
focusing
on
a
rationally
designed,
modular,
tunable
CPU
developed
our
laboratory.
A
significant
problem
thwarting
conventional
designs
is
paradox
between
broad
reactivity
stereoselectivity;
that
is,
while
enhanced
stereoselectivity
may
be
achieved
introducing
elements
close
N
atom,
concomitant
increase
local
steric
hindrance
often
limits
catalytic
activity
scope.
Our
newly
features
rigid
[6-5-3]
fused-ring
framework
spirocyclic
ketal
side
wall.
The
well-defined
three-dimensional
structure
minimizes
(inner
layer)
tunes
peripheral
environment
(outer
remote
substituents,
securing
stereoselectivity.
Different
chelating
were
readily
assembled
using
structural
module,
with
applications
mechanistically
diverse
transition-metal-catalyzed
reactions.
Thus,
series
2,2′-bipyridine
successfully
employed
general,
efficient,
highly
enantioselective
nickel-catalyzed
intermolecular
reductive
addition,
Ullmann
coupling
ortho-chlorinated
aryl
aldehydes,
carboxylation
benzylic
(pseudo)halides
CO2.
Notably,
these
exhibited
superior
reactions
compared
common
N-based
iridium-catalyzed
C–H
borylation
was
N,B-bidentate
ligand.
Furthermore,
challenging,
additive-free,
broad-scope
transfer
hydrogenative
direct
amination
half-sandwich
iridium
catalyst
supported
N,C-bidentate
excellent
performance
high
stereoselectivity,
which,
when
combined
experimental
computational
mechanistic
investigations,
"double-layer
control"
design
concept.Considering
described
herein
should
inspire
creation
novel
catalysts
drive
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(26), P. 17606 - 17612
Published: May 23, 2024
We
report
a
highly
cross-
and
atroposelective
coupling
between
ortho-(chloro)arylphosphine
oxides
ortho-(bromo)aryl
ethers.
This
previously
unknown
asymmetric
nickel-catalyzed
reaction
offers
direct
route
to
enantioenriched
axially
chiral
biaryl
monophosphine
that
are
difficult
access
by
other
means.
These
products
can
be
readily
reduced
generate
MOP-type
ligands
bearing
complex
skeletal
backbones.
The
utility
of
these
in
catalysis
is
also
demonstrated.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(49), P. 25714 - 25718
Published: Oct. 1, 2021
By
using
diazonaphthoquinones
and
anilines
as
key
reagents
through
a
point-to-axis
chiral
transfer
strategy,
the
atroposelective
synthesis
via
asymmetric
C(sp2
)-H
bond
insertion
reaction
of
arenes
has
been
realized
under
rhodium
catalysis,
providing
resulting
biaryl
atropisomers
in
moderate
to
excellent
yields
with
good
enantiomeric
ratios
(up
99:1).
Further
elaboration
indicates
this
type
axially
scaffold
may
have
promising
potentials
developing
novel
ligands.
Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
134(46)
Published: Sept. 23, 2022
Abstract
Organic
solvent
nanofiltration
(OSN)
is
an
emerging
membrane
separation
technology,
which
urgently
requires
robust,
easily
processed,
OSN
membranes
possessing
high
permeance
and
small
solutes‐selectivity
to
facilitate
enhanced
industrial
uptake.
Herein,
we
describe
the
use
of
two
2,2′‐biphenol
(BIPOL)
derivatives
fabricate
hyper‐crosslinked,
microporous
polymer
nanofilms
through
IP.
Ultra‐thin,
defect‐free
polyesteramide/polyester
(≈5
nm)
could
be
obtained
readily
due
relatively
large
molecular
size
ionized
nature
BIPOL
monomers
retarding
rate
The
microporosity
arises
from
hyper‐crosslinked
network
structure
monomer
rigidity.
Specifically,
amino‐BIPOL/PAN
exhibits
extraordinary
permselectivity
performances
with
weight
cut‐off
as
low
233
Da
MeOH
≈13
LMH/bar.
Precise
dye
mixtures
similar
M.W.
based
on
both
their
charge
are
achieved.
