Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
135(6)
Published: Dec. 12, 2022
Abstract
Chiral
α‐substituted
ethylphosphonate
and
ethylphosphine
oxide
compounds
are
widely
used
in
drugs,
pesticides,
ligands.
However,
their
catalytic
asymmetric
synthesis
is
still
rare.
Of
the
only
hydrogenation
methods
available
at
present,
all
cases
use
rare
metal
catalysts.
Herein,
we
report
an
efficient
earth‐abundant
transition‐metal
nickel
catalyzed
affording
corresponding
chiral
products
with
up
to
99
%
yield,
96
ee
(enantiomeric
excess)
(99
ee,
after
recrystallization)
1000
S/C
(substrate/catalyst);
this
also
first
study
on
of
terminal
olefins
using
a
catalyst
under
hydrogen
atmosphere.
The
mechanism
was
investigated
via
deuterium‐labelling
experiments
calculations
which
indicate
that
two
added
atoms
come
from
gas.
Additionally,
it
believed
reaction
involves
Ni
II
rather
than
0
cyclic
process
based
weak
attractive
interactions
between
olefin
substrate.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(6)
Published: Dec. 12, 2022
Chiral
α-substituted
ethylphosphonate
and
ethylphosphine
oxide
compounds
are
widely
used
in
drugs,
pesticides,
ligands.
However,
their
catalytic
asymmetric
synthesis
is
still
rare.
Of
the
only
hydrogenation
methods
available
at
present,
all
cases
use
rare
metal
catalysts.
Herein,
we
report
an
efficient
earth-abundant
transition-metal
nickel
catalyzed
affording
corresponding
chiral
products
with
up
to
99
%
yield,
96
ee
(enantiomeric
excess)
(99
ee,
after
recrystallization)
1000
S/C
(substrate/catalyst);
this
also
first
study
on
of
terminal
olefins
using
a
catalyst
under
hydrogen
atmosphere.
The
mechanism
was
investigated
via
deuterium-labelling
experiments
calculations
which
indicate
that
two
added
atoms
come
from
gas.
Additionally,
it
believed
reaction
involves
NiII
rather
than
Ni0
cyclic
process
based
weak
attractive
interactions
between
Ni
olefin
substrate.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(21), P. 14213 - 14220
Published: Oct. 21, 2023
A
chiral
nickel
complex
that
catalyzed
asymmetric
transfer
hydrogenation
of
α-substituted
acrylic
acids
under
mild
conditions
and
avoided
the
use
high-pressure
hydrogen
gas
was
developed.
The
products
included
β-amino
α-methyl
carboxylic
such
as
three
nonsteroidal
anti-inflammatory
profens.
Deuterium-labeling
experiments
DFT
studies
pointed
to
an
unconventional
protonation
a
metalacyclopropane
formed
by
α-phenylacrylic
acid
which
bonded
with
formic
acid.
An
alternative
conventional
pathway
hydride
insertion
cannot
explain
selective
deuteration
at
β-position
when
HCO2D
used.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(51)
Published: Oct. 27, 2022
In
contrast
to
previous
approaches
chiral
α-aryl
carboxylic
acids
that
based
on
reactions
using
hazardous
gases,
pressurized
setup
and
mostly
noble
metal
catalysts,
in
this
work,
a
nickel-catalyzed
general,
efficient
highly
enantioselective
carboxylation
reaction
of
racemic
benzylic
(pseudo)halides
under
mild
conditions
atmospheric
CO2
has
been
developed.
A
unique
2,2'-bipyridine
ligand
named
Me-SBpy
featuring
compact
polycyclic
skeleton
enabled
both
high
reactivity
stereoselectivity.
The
utility
method
demonstrated
by
synthesis
various
(30
examples,
up
95
%
yield
99
:
1
er),
including
profen
family
anti-inflammatory
drugs
transformations
the
as
key
intermediates.
Based
mechanistic
experimental
results,
plausible
catalytic
cycle
involving
Ni-complex/radical
equilibrium
Lewis
acid-assisted
activation
proposed.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: June 28, 2024
Abstract
Transition
metal-catalyzed
asymmetric
hydrogenation
is
one
of
the
most
efficient
methods
for
preparation
chiral
α-substituted
propionic
acids.
However,
research
on
this
method,
employing
cleaner
earth-abundant
metal
catalysts,
still
insufficient
in
both
academic
and
industrial
contexts.
Herein,
we
report
an
nickel-catalyzed
acrylic
acids
affording
corresponding
with
up
to
99.4%
ee
(enantiomeric
excess)
10,000
S/C
(substrate/catalyst).
In
particular,
method
can
be
used
obtain
(
R
)-dihydroartemisinic
acid
99.8:0.2
dr
(diastereomeric
ratio)
5000
S/C,
which
essential
intermediate
antimalarial
drug
Artemisinin.
The
reaction
mechanism
has
been
investigated
via
experiments
DFT
(Density
Functional
Theory)
calculations,
indicate
that
protonolysis
C-Ni
bond
key
intramolecular
proton
transfer
from
carboxylic
group
substrate,
rate-determining
step.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(10), P. 2786 - 2792
Published: Jan. 1, 2024
A
Ni-catalyzed
highly
enantioselective
hydrogenation
of
α,β-unsaturated
sulfones
was
successfully
realized
achieving
high
yields
(91–98%)
and
excellent
enantioselectivities
(up
to
99.9%
ee).
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(23), P. 3135 - 3156
Published: Aug. 13, 2024
Comprehensive
Summary
Transition
metal‐catalyzed
asymmetric
hydrogenation
is
an
efficient
and
direct
synthetic
method
to
access
chiral
compounds,
which
features
simplicity,
easy
working‐up
process,
high
atomic
economy.
It
typically
relies
on
precious
transition
metal
catalytic
systems,
including
ruthenium,
rhodium,
iridium
palladium,
always
face
the
difficulties
of
limited
resources,
cost,
environmental
contamination.
Therefore,
great
efforts
were
made
apply
earth‐abundant,
low
(non‐)toxic,
environmentally
friendly
metals,
such
as
iron,
cobalt,
nickel
copper,
in
past
decades,
some
considerable
breakthroughs
have
been
obtained.
In
this
review,
we
mainly
summarized
recent
research
progress
nickel‐catalyzed
prochiral
unsaturated
molecules,
olefins,
imines
ketones.
And
continuous
development
systems
application
them
into
challenging
prospected
future.
Key
Scientists
has
regarded
important
approach
molecules.
The
first
example
homogeneous
was
developed
by
Knowles
Horner
1968,
respectively.
1971,
Kagan
privileged
DIOP
ligand
for
hydrogenation.
Halpern
Brown
deep
studies
Rh‐catalyzed
1977,
Noyori
a
powerful
BINAP
1980.
Owing
Noyori's
contribution
field
hydrogenation,
they
awarded
Nobel
Prize
Chemistry
2001.
1984,
Ohkubo
pioneering
earth‐abundant
Ni‐catalyzed
ethyl
α‐methylcrotonate.
A
many
scientists
tremendous
ligands,
as,
Bosnich,
Kumada,
Giongo,
Takaya,
Miyashima,
Achiwa,
Burk,
Pflaltz,
Chan,
X.
Zhang,
Imamoto,
Zhou,
Genet,
Sannicolo,
Ding,
Hoge,
W.
Z.
Tang,
these
ligands
owned
wide
addition,
Fan
investigation
aromatic
heterocyclic
compounds.
importance
(transfer)
promoted
cheap
researchers,
Hamada,
Gao,
J.
S.
Chirik,
Y.‐G.
Lv,
Dong,
Fu,
Deng,
Hou,
there
are
other
that
also
transformation,
with
too
space
list
all
them.
Asian Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
13(7)
Published: May 11, 2024
Abstract
A
pressure
gauge
was
incorporated
into
a
two‐chamber
glass
H‐tube
to
continuously
monitor
the
inside
reactor
when
working
with
gases.
The
ex
situ
generated
H
2
,
D
acetylene
and
CO
were
tested
in
reactors,
calibration
curves
plotted.
series
of
unsaturated
compounds
two
or
more
double
C=C
bonds
accessible
for
hydrogenation
synthesized
hydrogenation.
proceeded
well
due
constant
control,
desired
products
isolated
good
yields.
same
procedures
then
carried
out
using
steel
autoclaves
verify
results
compare
them.
Surprisingly,
almost
obtained,
confirming
effectiveness
self‐made
reactors.
mechanism
further
investigated
D‐labeled
reagents.
kinetics
studied
both
manometric
reactors
autoclaves,
which
showed
similar
nature
main
process
reaction
units.
Thus,
created
can
be
effectively
used
barometric
transformations
instead
appropriate
cases.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 19, 2024
Despite
the
preliminary
success
of
transition
metal-catalyzed
[3+2]
annulation
amides
with
olefins,
corresponding
radical-type
remains
a
laborious
challenge.
Herein
we
report
first
photoredox-catalyzed
aromatic
olefins.
We
established
an
approach
to
generate
unprecedented
iminium
radicals
by
reducing
oxyiminium
intermediates,
formed
in
situ
from
Tf
