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,
Journal Year:
2023,
Volume and Issue:
135(35)
Published: June 12, 2023
Abstract
A
highly
chemoselective
earth‐abundant
transition
metal
copper
catalyzed
asymmetric
hydrogenation
of
C=O
bonds
exocyclic
α,β‐unsaturated
pentanones
was
realized
using
H
2
.
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.
Chinese Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
41(22), P. 2988 - 2994
Published: June 30, 2023
Comprehensive
Summary
The
design
and
synthesis
of
spirochroman‐2‐on‐4,1'‐indan‐7'‐ol
(SCIOL)
its
application
for
synthesizing
chiral
monophosphinite
ligands
are
reported.
features
a
tandem
double
Friedel‐Crafts
reaction/lactonization
to
construct
the
spiro
framework
desired
racemic
SCIOL
was
obtained
via
6
steps
with
total
yield
44.5%.
Using
an
inclusion
resolution
N
‐benzylcinchonidinium
chloride,
optical
could
be
in
good
yields
on
gram
scale.
preliminary
studies
indicated
that
corresponding
exhibit
high
catalytic
activity
enantioselectivity
(up
94%
ee)
rhodium‐catalyzed
asymmetric
hydrogenation
‐acetyl
dehydroamino
esters.
These
outcomes
highlight
significant
potential
as
useful
development
ligands.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(10), P. 6631 - 6638
Published: May 2, 2024
This
article
is
a
history
of
an
industrial-academic
partnership
that
started
almost
two
decades
ago
and
details
the
evolution
relationship
between
small
academic
research
group
spin-out
company
located
in
Portugal.
Their
activities
have
ranged
from
development
new
metal-based
catalytic
systems
for
asymmetric
epoxidations,
allylic
alkylations,
arylations
to
novel
cinchona-based
organocatalysts
hydrosilylations
Michael
additions.
Current
common
interests
are
centered
on
chiral
Natural
Deep
Eutectic
Solvent
systems,
which
they
investigating
different
types
reaction
systems.
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(31), P. 6362 - 6369
Published: Jan. 1, 2024
A
small
library
of
easily
prepared
diamidophosphite-sulfides
based
on
1,3-thioether
alcohols,
primarily
terpenoid
nature,
was
developed.
Upon
complexation
with
Pd(II)
ions,
these
hemilabile
ligands
showed
the
ability
to
form
both
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(26)
Published: Feb. 27, 2023
Abstract
Die
enantioselektive
Hydrierung
von
cyclischen
Enamiden
wurde
mit
einem
Cobalt‐Bisphosphin‐Katalysator
erreicht.
Reduktion
verschiedenster
dreifach
substituierter
carbocyclischen
Enamide
zu
den
entsprechenden
gesättigten
Amiden
erfolgte
hoher
Aktivität
und
ausgezeichneter
Enantioselektivität
(bis
99
%)
unter
Verwendung
des
Systems
CoCl
2
/(
S
,
)‐Ph‐BPE.
Methode
lässt
sich
auf
die
Synthese
chiraler
Amine
durch
eine
basische
Hydrolyse
der
Hydrierungsprodukte
ausweiten.
Erste
mechanistische
Untersuchungen
deuten
Anwesenheit
einer
high‐spin
Cobalt(II)‐Spezie
im
katalytischen
Cyclus
hin.
Wir
postulieren
Kohlenstoff‐Kohlenstoff‐Doppelbindung
über
einen
Sigma‐Bindungs‐Metathese‐Weg.
Research Square (Research Square),
Journal Year:
2023,
Volume and Issue:
unknown
Published: July 5, 2023
Abstract
Given
the
high
demand
for
organophosphorus
compounds
(OPCs),
developments
of
sustainable
routes
toward
OPCs
synthesis
attract
much
attention.
Numerous
efforts
are
contributing
to
P
4
transformations
into
1
chemistry.
Nevertheless,
existing
methods
necessitate
energy-immense
multisteps
often
utilize
corrosive
and
dangerous
reagents
originating
from
/P
red
allotropes,
harmful
intermediates,
chemical
waste,
impeding
further
exploration
practical
applications.
Herein,
direct
efficient
transformation
inorganic
phosphates
[TBA][H
2
PO
]
is
demonstrated.
These
salts
were
activated
by
cost-efficient
oxalyl
chloride
at
20°C
in
5
minutes,
through
a
double
chlorination
OH
on
phosphorus
upon
elimination
CO
molecules,
followed
reducing
resultant
intermediate
with
trichlorosilane,
then
coupling
haloaryls
under
palladium-catalysis
provide
desired
OPCs.
Diverse
tolerance
various
functionalities
aryl
halides
achieved
potential
scale-up
industrial
applications,
eliminating
reliance
extortionate,
problematic
allotropes.
X-ray
diffraction
DFT
calculations
revealed
[TBA][PO
Cl
].
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.