Chemistry - A European Journal,
Journal Year:
2023,
Volume and Issue:
29(28)
Published: March 8, 2023
A
set
of
16
chiral
ruthenium
complexes
containing
atropisomerically
stable
N-Heterocyclic
Carbene
(NHC)
ligands
was
synthesized
from
prochiral
NHC
precursors.
After
a
rapid
screening
in
asymmetric
ring-opening-cross
metathesis
(AROCM),
the
most
effective
atrop
BIAN-NHC
Ru-catalyst
(up
to
97
:
3
er)
then
converted
Z-selective
catechodithiolate
complex.
The
latter
proved
be
highly
efficient
AROCM
exo-norbornenes
affording
valuable
trans-cyclopentanes
with
excellent
Z-selectivity
(>98
%)
and
high
enantioselectivity
96.5
3.5
er).
Chemical Science,
Journal Year:
2021,
Volume and Issue:
12(31), P. 10583 - 10589
Published: Jan. 1, 2021
We
report
novel,
sterically-bulky,
easily-accessible
NHC
ligands
based
on
the
hash
peralkylation
concept.
The
new
have
been
commercialized
in
collaboration
with
Millipore
Sigma:
IPr#HCl,
915653;
Np#HCl;
915912;
BIAN-IPr#HCl,
916420.
Inorganic Chemistry,
Journal Year:
2022,
Volume and Issue:
61(4), P. 2105 - 2118
Published: Jan. 14, 2022
A
series
of
heteroleptic
square-planar
Pt
and
Pd
complexes
with
bis(diisopropylphenyl)
iminoacenaphtene
(dpp-Bian)
Cl,
1,3-dithia-2-thione-4,5-dithiolate
(dmit),
or
1,3-dithia-2-thione-4,5-diselenolate
(dsit)
ligands
have
been
prepared
characterized
by
spectroscopic
techniques,
elemental
analysis,
X-ray
diffraction
cyclic
voltammetry
(CV).
The
intermolecular
noncovalent
interactions
in
the
crystal
structures
were
assessed
density
functional
theory
(DFT)
calculations.
anticancer
activity
breast
cancer
cell
lines
was
limited
their
solubility.
Pd(dpp-Bian)
dmit
dsit
as
well
an
uncoordinated
dpp-Bian
ligand
devoid
cytotoxicity,
while
[Pd(dpp-Bian)Cl2]
complex
cytotoxic.
On
contrary,
all
Pt(dpp-Bian)
demonstrated
a
low
micromolar
concentration
range,
which
8–20
times
higher
than
cisplatin,
up
to
2.5-fold
selectivity
toward
cells
over
healthy
fibroblasts.
presence
redox-active
resulted
induction
reactive
oxygen
species
(ROS)
cells.
In
addition,
these
able
intercalate
into
DNA,
indicating
dual
mechanism
action.
ChemCatChem,
Journal Year:
2021,
Volume and Issue:
14(1)
Published: Sept. 28, 2021
α-Diimine
ligands
have
significantly
shaped
the
coordination
chemistry
of
most
transition
metal
complexes.
Among
them,
bis(imino)acenaphthene
(BIANs)
recently
been
matured
to
great
versatility
and
applicability
catalytic
reactions.
Besides
variations
ligand
periphery,
BIAN
resides
within
their
ability
undergo
facile
electronic
manipulations.
This
review
highlights
key
aspects
in
complexes
summarizes
recent
contributions
metal-BIAN
catalysts
syntheses
small
functionalized
organic
molecules.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(17)
Published: Feb. 10, 2022
Abstract
In
the
past
years,
Pd
0
‐catalyzed
C(sp
3
)−H
activation
provided
efficient
and
step‐economical
methods
to
synthesize
carbo‐
heterocycles
via
direct
2
)−C(sp
)
bond
formation.
We
report
herein
that
a
1,4‐Pd
shift
allows
access
N‐heterocycles
which
are
difficult
build
reaction.
It
is
shown
o
‐bromo‐
N
‐methylanilines
undergo
at
‐methyl
group,
followed
by
intramolecular
trapping
or
another
nitrogen
substituent
remote
C−C
formation
generate
biologically
relevant
isoindolines
β‐lactams.
The
product
selectivity
influenced
employed
ligand,
with
NHCs
favoring
of
coupling
against
products
arising
from
N‐demethylation.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(29), P. 16077 - 16084
Published: April 26, 2021
Abstract
The
transition‐metal‐catalyzed
C−N
cross‐coupling
has
revolutionized
the
construction
of
amines.
Despite
innovations
multiple
generations
ligands
to
modulate
reactivity
metal
center,
for
low‐temperature
enantioselective
amination
aryl
halides
remain
a
coveted
target
catalyst
engineering.
Designs
that
promote
one
elementary
reaction
often
create
bottlenecks
at
other
steps.
We
here
report
an
unprecedented
(as
low
as
−50
°C),
Ni‐catalyzed
chlorides
with
sterically
hindered
secondary
amines
via
kinetic
resolution
process
(s
factor
up
>300).
A
bulky
yet
flexible
chiral
N‐heterocyclic
carbene
(NHC)
ligand
is
leveraged
drive
both
oxidative
addition
and
reductive
elimination
barriers
control
enantioselectivity.
Computational
studies
indicate
rotations
σ‐bonds
on
C
2
‐symmetric
adapt
changing
needs
catalytic
processes.
expect
this
design
would
be
widely
applicable
diverse
transition
states
achieve
challenging
metal‐catalyzed
asymmetric
reactions.
