Chiral
phospholane
ligands
and
catalysts
have
been
widely
applied
in
asymmetric
catalysis
synthesis.
However,
the
construction
of
chiral
skeleton
remains
challenging
primarily
relies
on
use
auxiliaries
or
resolution.
In
this
work,
a
highly
enantioselective
diastereoselective
synthesis
P-stereogenic
oxides
has
achieved
through
cobalt-catalyzed
desymmetric
hydroalkylation
strategy.
This
method
enables
two
discrete
stereocenters
with
excellent
yields
enantiomeric
excesses.
Angewandte Chemie International Edition,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 6, 2025
Abstract
Electrochemical,
fully
stereoselective
P(V)‐radical
hydrophosphorylation
of
olefins
and
carbonyl
compounds
using
a
P(V)
reagent
is
disclosed.
By
strategically
selecting
the
anode
material,
radical
reactivity
accessible
for
alkene
whereas
polar
pathway
operates
ketone
hydrophosphorylation.
The
mechanistic
intricacies
these
chemoselective
transformations
were
explored
in‐depth.
A
series
of
chiral
hybrid
diphosphorus
ligands
incorporating
a
conformationally
flexible
tropos
diphenylmethane-based
phosphoramidite
unit
have
been
developed
and
evaluated
in
the
Rh-catalyzed
asymmetric
hydrogenation
2-(1-arylvinyl)anilides
α-enamides,
leading
to
up
>99%
yield
99%
enantiomeric
excess.
Preliminary
results
from
comparative
studies
showcased
extraordinary
catalytic
performance
these
phosphine–phosphoramidite
ligands,
with
competency
essentially
superior
those
well-established
regular
rigid
backbone.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 28, 2025
A
novel
chiral
ligand,
named
MAdPHOS,
bearing
a
P-stereogenic
phosphane
and
diadamantyl
linked
by
NH
bridge
has
been
synthesized.
This
bulky,
C1-symmetric,
PNP
ligand
prepared
from
enantiopure
tert-butylmethyl
aminophosphane
was
obtained
as
crystalline
solid.
The
NH/PH
tautomerism,
air-stability,
σ-donor
capacity
of
MAdPHOS
have
assessed
herein.
free
prepared,
showing
much
higher
stability,
in
the
solid
form,
than
its
tert-butyl
analogue
MaxPHOS.
Both
rhodium
nickel
COD
complexes
prepared.
Rh-MAdPHOS
complex
shown
outstanding
enantioselectivities
asymmetric
hydrogenation
enamides.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Сен. 25, 2024
A
series
of
polymeric
chiral
diamine
ligands
are
developed
by
diboron-templated
asymmetric
reductive
couplings,
and
their
iridium
complexes
Ir-polydiamines
efficient
recyclable
catalysts
for
transfer
hydrogenation
(ATH)
functionalized
ketones,
affording
a
optically
active
secondary
alcohols
in
excellent
enantioselectivities
(up
to
99%
ee)
unprecedentedly
high
total
TONs
(12,000,
six
cycles).
Ir-polydiamine
with
longer
chains
offered
higher
reactivities,
providing
plausible
deactivation
mechanism
practical
solutions
ATH
vitamin
B5
phenylephrine.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 17, 2025
This
work
introduces
a
novel
Mn(I)-catalyzed
enantioselective
alkylation
methodology
that
efficiently
produces
wide
array
of
P-chiral
phosphines
with
outstanding
yields
and
enantioselectivities.
Notably,
the
exceptional
reactivity
Mn(I)
complexes
in
these
reactions
is
demonstrated
by
their
effective
catalysis
both
typically
reactive
alkyl
iodides
bromides,
as
well
less
chlorides.
approach
broadens
accessibility
to
various
simplifies
synthesis
chiral
tridentate
pincer
concise
1–2
step
process,
contrary
conventional,
labor-intensive
multistep
procedures.
Importantly,
development
significantly
expands
applicability
earth-abundant
Mn(I)-based
beyond
recently
established
roles
catalytic
hydrogenative
conjugate
addition
reactions,
emphasizing
potential
viable
alternative
noble
metal
chemistry
and,
some
cases,
even
surpassing
performance.
Chemical Science,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
provides
an
overview
of
predictive
tools
in
asymmetric
synthesis.
The
evolution
methods
from
simple
qualitative
pictures
to
complicated
quantitative
approaches
is
connected
with
the
increased
complexity
stereoselective
Chemistry - A European Journal,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 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.