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.
The Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
87(15), P. 10146 - 10157
Published: July 13, 2022
A
mild
and
facile
photo-induced
cascade
radical
addition/cyclization
of
unactivated
alkenes
has
been
reported,
through
which
a
variety
biologically
valuable
phosphine-containing
quinazolinones
could
be
obtained
in
moderate
to
good
yields.
The
protocol
was
characterized
by
conditions,
broad
substrate
scope,
high
atomic
economy.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(26)
Published: Feb. 27, 2023
The
enantioselective
hydrogenation
of
cyclic
enamides
has
been
achieved
using
an
earth-abundant
cobalt-bisphosphine
catalyst.
Using
CoCl2
/(S,S)-Ph-BPE,
several
trisubstituted
carbocyclic
were
reduced
with
high
activity
and
excellent
enantioselectivity
(up
to
99
%)
the
corresponding
saturated
amides.
methodology
can
be
extended
synthesis
chiral
amines
by
base
hydrolysis
products.
Preliminary
mechanistic
investigations
reveal
presence
a
spin
cobalt
(II)
species
in
catalytic
cycle.
We
propose
that
carbon-carbon
double
bond
proceeds
via
sigma-bond-metathesis
pathway.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(35)
Published: June 12, 2023
A
highly
chemoselective
earth-abundant
transition
metal
copper
catalyzed
asymmetric
hydrogenation
of
C=O
bonds
exocyclic
α,β-unsaturated
pentanones
was
realized
using
H2
.
The
desired
products
were
obtained
with
up
to
99
%
yield
and
96
ee
(enantiomeric
excess)
(99
ee,
after
recrystallization).
corresponding
chiral
allylic
pentanol
can
be
converted
into
several
bioactive
molecules.
mechanism
investigated
via
deuterium-labelling
experiments
control
experiments,
which
indicate
that
the
keto-enol
isomerization
rate
substrate
is
faster
than
also
show
Cu-H
complex
only
catalyze
chemoselectively
reduction
carbonyl
group.
Computational
results
multiple
attractive
dispersion
interactions
(MADI
effect)
between
catalyst
bulky
substituents
play
important
roles
stabilize
states
reduce
generation
by-products.
Chemistry - A European Journal,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 1, 2025
Phosphine-
or
carbene-based
soft
ligands
are
customarily
used
in
Rh
and
other
late
transition
metal
catalyzed
alkene
alkyne
hydrosilylation
hydrogenation.
We
report
here
an
aziridine
a
2-pyrrolidone
with
pyridyl
sidearms,
whose
cationic
Rh(I)
complexes
prove
as
excellent
catalysts
for
hydrosilylating
terminal
olefins
by
Et3SiH
giving
anti-Markovnikov
products
selectively.
To
the
best
of
our
knowledge,
[(2-pyrrolidone)-Rh]+
seems
to
be
most
active
catalyst
recording
highest
TOF
24000
h-1.
It
works
remarkably
(TOF:
714
h-1)
even
at
10
ppm
concentration!
Terminal
alkynes
hydrosilylated
too
give
β-(Z)-vinylsilanes
Both
also
hydrogenate
alkenes
doubly-hydrogenate
alkynes,
both
internal,
under
ambient
benchtop
conditions.
But
hydrogenation,
[(aziridine)-Rh]+
better.
air-stable.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 15, 2025
A
new
class
of
chiral
spiro
monophosphinites,
based
on
a
unique
non-C2-symmetric
3-oxo-1,1'-spirobiindane
scaffold
featuring
large
dihedral
angle,
has
been
effectively
designed
and
synthesized.
From
readily
accessible
resources,
these
monophosphinites
were
synthesized
via
eight
steps
in
16-32%
yields.
Their
excellent
performance
the
rhodium-catalyzed
asymmetric
hydrogenation
β-dehydroamino
acid
esters
underscores
critical
impact
angle
enhancing
activity
enantioselectivity.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(12), P. 3436 - 3441
Published: Jan. 1, 2024
The
highly
enantioselective
hydrogenation
of
allylic
sulfones
catalyzed
by
Rh-(
R
,
)-f-spiroPhos
for
synthesis
chiral
β-ester
has
been
developed
the
first
time
achieving
high
yields
and
excellent
enantioselectivities
(92–99.9%
ee).
This
review
highlights
the
progress
achieved
in
transition-metal
(ruthenium,
rhodium,
iridium,
and
nickel)
catalyzed
asymmetric
hydrogenation
of
unsaturated
sulfones
including
substrate
scopes,
catalytic
mechanisms,
applications.
