Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 17, 2024
Comprehensive
Summary
Terpyridine
ligands
have
been
applied
as
a
class
of
unique
due
to
their
rich
coordination
chemistry
in
the
catalysis.
Herein,
we
developed
new
C
2
‐symmetric
chiral
terpyridine‐pyrroloimidazolone
(TPy‐BPI).
Their
catalytic
activity
was
evaluated
asymmetric
Friedel‐Crafts
alkylation
indoles
with
2,3‐dioxopyrrolidines.
Excellent
yields
(up
92%)
and
high
enantioselectivities
97%
ee)
are
obtained
for
wide
range
substrates
under
mild
conditions.
In
addition
2,3‐dioxopyrrolidines,
β
,
γ
‐unsaturated
α
‐ketoesters
were
also
compatible
Ni(OTf)
‐TPy‐BPI
ligand
L1
‐catalyzed
reaction.
Control
experiments,
single
crystal
structure
two
TPy‐BPI
‐Ni(OTf)
complexes,
DFT
calculations
revealed
origins
enantioselectivity.
To
best
our
knowledge,
work
is
first
report
showing
that
terpyridine
framework
contained
only
nitrogen
atoms
coordinating
metal,
additional
pyridine
unit
acted
stereodirecting
element,
which
different
from
previously
reported
containing
all
three
metal.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(47)
Опубликована: Окт. 16, 2023
Abstract
Catalytic
asymmetric
transformations
by
dearomatization
have
developed
into
a
widely
applicable
synthetic
strategy,
but
heavily
relied
on
the
use
of
arenes
bearing
heteroatom.
In
this
case,
is
facilitated
involvement
p
‐orbital
electron
Different
from
conventional
substrate‐dependent
model,
here
we
demonstrate
that
activation
d
transition‐metal
center
can
serve
as
driving
force
for
dearomatization,
and
applied
to
development
novel
alkynyl
copper
remote
substitution
reaction.
A
newly
modified
PyBox
chiral
ligand
enables
construction
valuable
diarylmethyl
triarylmethyl
skeletons
in
high
enantioselectivities.
An
unexpected
tandem
process
involving
sequential
substitution/cyclization/1,5‐H
shift
leads
formation
enantioenriched
C−N
axis.
gram‐scale
reaction
various
downstream
highlight
robustness
method
potential
products.
Preliminary
mechanistic
studies
reveal
mononuclear
Cu‐catalyzed
process.
ACS Catalysis,
Год журнала:
2024,
Номер
14(12), С. 9244 - 9253
Опубликована: Июнь 3, 2024
Catalytic
asymmetric
dearomatization
(CADA)
is
a
powerful
tool
for
the
rapid
construction
of
complex
chiral
three-dimensional
cyclic
molecules
featuring
quaternary
carbon
centers
from
readily
available
arenes.
However,
ubiquitous
nonfunctionalized
1-naphthols
to
afford
remains
challenging
and
undeveloped.
This
study
reports
dearomative
[4
+
1]
spiroannulation
via
copper
catalysis.
reaction
features
highly
chemo-,
regio-,
stereoselective
nucleophilic
addition
intramolecular
annulation
cascade
reactive
π-extended
copper-allenylidene,
thus
enabling
practical
synthesis
range
valuable
spirocyclic
enones
bearing
stereocenter
with
high
efficiency.
Furthermore,
this
protocol
applicable
phenols.
Control
experiments
supported
substitution-annulation
mechanism
by
excluding
process
involving
1,3-sigmatropic
shift.
Preliminary
biological
activity
studies
indicated
that
synthesized
hold
significant
promise
as
anticancer
agents
inducing
tumor
cell
apoptosis.
ACS Catalysis,
Год журнала:
2024,
Номер
14(12), С. 9254 - 9264
Опубликована: Июнь 3, 2024
Catalytic
asymmetric
dearomatization
reactions
of
α-unsubstituted
β-naphthols
are
very
challenging
due
to
the
high
energy
barrier
resulting
from
loss
aromaticity.
Herein,
we
describe
an
example
enantioselective
catalytic
dearomative
spiroannulation
with
yne-allylic
esters.
The
success
this
reaction
relied
on
copper-catalyzed
remote
strategy
using
esters
as
bis-electrophilic
reagents.
This
transformation
features
mild
conditions,
broad
functional
group
tolerance,
and
extensive
substrate
scope,
thereby
facilitating
efficient
construction
array
enantioenriched
naphthalene-2-one
spiroindolenine
derivatives.
Experimental
studies
density
theory
calculations
establish
pathway
origin
stereoselectivity.
ACS Catalysis,
Год журнала:
2023,
Номер
13(9), С. 6301 - 6311
Опубликована: Апрель 24, 2023
Catalytic
enantioselective
azide–alkyne
cycloaddition
(E-AAC)
is
a
highly
efficient
click
technology
for
the
construction
of
structurally
diverse
chiral
triazoles,
which
have
broad
applications
in
fields
synthetic
chemistry,
medicinal
biological
and
materials
science.
The
past
six
years
seen
impressive
developments
copper-,
nickel-,
iridium-,
rhodium-catalyzed
E-AAC
reactions.
This
review
provides
brief
summary
on
this
evolution
according
to
different
strategies
implemented.
ACS Applied Materials & Interfaces,
Год журнала:
2024,
Номер
16(4), С. 5158 - 5167
Опубликована: Янв. 19, 2024
Flow
chemistry
provides
a
neo-orientation
for
the
research
and
development
of
chemical
technology,
in
which
heterogeneous
continuous
catalysis
based
on
packed
beds
can
realize
rapid
separation
recycling.
However,
options
catalysts
are
still
limited.
In
this
work,
we
gradually
grow
covalent
organic
frameworks
(COFs,
TpBpy)
surface
silica
gel
(SiO2)-supported
substrate
to
obtain
stable
copper(I)-chelated
high-loading
catalyst
(SiO2@CuI-TpBpy).
SiO2@CuI-TpBpy
shows
high
catalytic
activity
three-component
Huisgen
1,3-dipolar
cycloaddition,
giving
corresponding
triazoles
with
excellent
yields
reposeful
recyclability
under
batch
conditions.
The
structures
remain
steady,
copper
contents
basically
unchanged
after
five
cycles.
Then,
successfully
applied
one-pot
flow
prepare
rufinamide
89%
yield
24
h
stably
efficiently
mere
traces
ions
remaining.
More
importantly,
system
reveals
minuscule
effect
particle
size
internal
diffusion.
This
COF
encapsulation
strategy
presents
new
possibility
design
industrial
metal
loading
low
diffusion
resistance.
Chemical Science,
Год журнала:
2024,
Номер
15(16), С. 5993 - 6001
Опубликована: Янв. 1, 2024
Axially
chiral
molecular
scaffolds
are
widely
present
in
therapeutic
agents,
natural
products,
catalysts,
and
advanced
materials.
The
construction
of
such
molecules
has
garnered
significant
attention
from
academia
industry.
catalytic
asymmetric
synthesis
axially
biaryls,
along
with
other
non-biaryl
molecules,
been
extensively
explored
the
past
decade.
However,
atroposelective
C-O
axial
chirality
remains
largely
underdeveloped.
Herein,
we
document
a
copper-catalyzed
compounds
using
novel
1,8-naphthyridine-based
ligands.
Mechanistic
investigations
have
provided
good
evidence
support
mechanism
involving
synergistic
interplay
between
desymmetrization
reaction
kinetic
resolution
process.
method
described
this
study
holds
great
significance
for
compounds,
promising
applications
organic
chemistry.
utilization
ligands
copper
catalysis
is
anticipated
to
find
broad
copper(i)-catalyzed
azide-alkyne
cycloadditions
(CuAACs)
beyond.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июнь 10, 2024
Chiral
1,2,3-triazoles
are
highly
attractive
motifs
in
various
fields.
However,
achieving
catalytic
asymmetric
click
reactions
of
azides
and
alkynes
for
chiral
triazole
synthesis
remains
a
significant
challenge,
mainly
due
to
the
limited
systems
substrate
scope.
Herein,
we
report
an
enantioselective
azidation/click
cascade
reaction
N-propargyl-β-ketoamides
with
readily
available
potent
azido
transfer
reagent
via
copper
catalysis,
which
affords
variety
up
99%
yield
95%
ee
under
mild
conditions.
Notably,
1,5-disubstituted
triazoles
that
have
not
been
accessed
by
previous
also
prepared
good
functional
group
tolerance.
