Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(5), P. 1176 - 1181
Published: Jan. 11, 2024
Abstract
An
N‐allylation
of
monosubstituted
acyl
hydrazines
with
allylic
alcohols
has
been
developed
by
using
B(C
6
F
5
)
3
catalysis.
This
protocol
allows
for
convenient
access
to
various
synthetically
useful
N‐allylated
hydrazine
products
in
48–96%
yields
broad
substrate
scope
and
wide
functional
group
compatibility.
The
operationally
simple
reaction
proceeds
without
calling
stringent
removal
air
moisture,
can
be
readily
scaled
up
gram
scale.
Preliminary
mechanistic
studies
support
the
generation
an
carbon
cation
that
is
involved
catalytic
cycle,
via
situ
formation
diallyl
ethers
as
intermediates.
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.
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.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 14, 2025
Herein
we
first
report
a
nickel-catalyzed
asymmetric
iterative
1,2-reduction
of
trisubstituted
enones
to
cycloalkanols
with
two
contiguous
stereocenters
in
high
yields
excellent
diastereo-
and
enantioselectivities
(36
examples,
up
98.5:1.5
er,
>20:1
dr,
TON
=
500).
The
combined
experimental
computational
mechanistic
studies
suggested
energy
changes
during
consecutive
reduction
processes
provided
range
unique
rationales
that
have
not
been
disclosed
hydrogenation-related
studies.
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).
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 27, 2024
Compared
with
chiral
β3-amino
phosphorus
compounds,
which
can
be
easily
derived
from
natural
optically
pure
α-amino
acids,
obtaining
β2-amino
derivatives
remains
a
challenge.
These
derivatives,
cannot
amino
possess
unique
biological
activities
or
potential
catalytic
activities.
Herein,
highly
enantioselective
hydrogenation
for
the
preparation
of
E-β-enamido
compounds
is
reported
by
using
green
and
low-cost
earth-abundant
metal
nickel
catalyst
(13
examples
99%
ee).
In
particular,
this
system
provides
same
enantiomer
product
E-
Z-alkene
substrates,
E/Z-substrate
mixtures
provide
good
results
(up
to
96%
The
products
diversely
derivatized,
exhibit
as
novel
β2-aminophosphine
ligands.
Density
functional
theory
calculations
reveal
that
weak
attractive
interactions
between
substrate
are
crucial
achieving
perfect
enantioselectivities.
addition,
different
coordination
modes
Z-substrates
may
result
in
formation
product.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(37), P. 15243 - 15254
Published: Jan. 1, 2024
A
novel
solvent-controlled
asymmetric
hydrogenation
protocol
was
developed.
Both
enantiomers
of
chiral
THQs
were
efficiently
synthesised
with
excellent
enantioselectivities.
Mechanistic
studies
reveal
the
origin
enantioselectivity.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(48), P. 8739 - 8744
Published: Nov. 28, 2023
A
nickel-catalyzed
chemoselective
asymmetric
transfer
hydrogenation
of
α,β-unsaturated
ketimines
using
ethanol
as
a
hydrogen
donor
under
mild
conditions
that
avoid
high-pressure
gas
was
developed.
With
this
catalyst,
C1-selective
deuterated
chiral
allylic
amines
were
efficiently
synthesized
only
stoichiometric
2-propanol-d8.
Mechanism
studies
demonstrated
the
formation
nickel
hydride
intermediate.
