Chemical Science,
Год журнала:
2024,
Номер
15(30), С. 12006 - 12016
Опубликована: Янв. 1, 2024
The
acid-mediated
cyclisation
of
sterically
encumbered
cyclic
triphosphanes
with
nitriles
provides
access
to
five-membered
cationic
and
neutral
P
3
CN
heterocycles
tuneable
colour.
ACS Catalysis,
Год журнала:
2023,
Номер
13(10), С. 6994 - 7001
Опубликована: Май 9, 2023
A
mechanism-inspired,
reaction
mode-controlled
enantio-
and
regioselective
anti-Markovnikov
hydrophosphination
of
unactivated
alkynes
was
accomplished
by
NiII
catalysis.
Alkenyl
phosphine
products
could
be
obtained
with
high
regio-
enantioselectivity
easily
derivatized
to
structurally
diverse
chiral
compounds.
Mechanistic
studies
on
both
Ni0-catalyzed
Markovnikov
addition
NiII-catalyzed
have
been
carried
out
combining
experimental
computational
methods.
In
the
Ni0
system,
an
allyl
nickel
complex
as
catalyst
resting
state
whose
structure
unambiguously
determined
single-crystal
XRD
analysis.
sequential
hydrometallation,
ligand
exchange,
reductive
elimination
mechanism
elucidated
corroboratively
DFT
calculations.
cationic
secondary
serves
active
catalyst.
migratory
insertion
protonation
sequence
operative
accomplish
hydrophosphination.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(36)
Опубликована: Июнь 19, 2023
We
describe
a
copper
catalyst
that
promotes
the
addition
of
phosphines
to
cyclopropenes
at
ambient
temperature.
A
range
cyclopropylphosphines
bearing
different
steric
and
electronic
properties
can
now
be
accessed
in
high
yields
enantioselectivities.
Enrichment
phosphorus
stereocenters
is
also
demonstrated
via
Dynamic
Kinetic
Asymmetric
Transformation
(DyKAT)
process.
combined
experimental
theoretical
mechanistic
study
supports
an
elementary
step
featuring
insertion
Cu
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(40)
Опубликована: Авг. 18, 2023
Herein,
a
copper(I)-catalyzed
asymmetric
hydrophosphination
of
3,3-disubstituted
cyclopropenes
is
reported.
It
provides
series
phosphine
derivatives
in
high
to
excellent
diastereo-
and
enantioselectivities.
The
methodology
enjoys
broad
substrate
scope
on
both
diarylphosphines.
stereoselectivity
attributed
the
stability
Cu(I)-(R,R)-QUINOXP*
complex
presence
stoichiometric
HPPh2
produced
phosphines,
high-performance
induction
complex.
Finally,
method
used
for
synthesis
new
chiral
phosphine-olefin
compounds
built
cyclopropane
skeleton,
one
which
serves
as
wonderful
ligand
Rh-catalyzed
conjugate
addition
phenylboronic
acid
various
α,β-unsaturated
compounds.
Molecules,
Год журнала:
2024,
Номер
29(3), С. 688 - 688
Опубликована: Фев. 1, 2024
Rare
earths,
scandium,
yttrium,
and
the
fifteen
lanthanoids
from
lanthanum
to
lutetium,
are
classified
as
critical
metals
because
of
their
ubiquity
in
daily
life.
They
present
magnets
cars,
especially
electric
cars;
green
electricity
generating
systems
computers;
steel
manufacturing;
glass
light
emission
materials
for
safety
lighting
lasers;
exhaust
catalysts
supports;
artificial
rubber
production;
agriculture
animal
husbandry;
health
cancer
diagnosis
treatment;
a
variety
electronic
products
essential
modern
living.
have
potential
replace
toxic
chromates
corrosion
inhibition,
magnetic
refrigeration,
new
materials,
role
may
expand.
This
review
examines
sustainability,
environment,
recycling,
crop
production,
feedstocks,
catalysis,
health,
well
considering
future
uses.
Organic Chemistry Frontiers,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
highlights
recent
advances
in
the
hydrofunctionalisation
of
cyclopropenes
through
formation
carbon–heteroatom
bonds
for
synthesis
polysubstituted
cyclopropanes.
Chemical Communications,
Год журнала:
2023,
Номер
59(10), С. 1258 - 1273
Опубликована: Янв. 1, 2023
An
examination
of
several
catalytic
reactions
among
the
group
15
elements
is
presented.
The
connections
between
chemistry
pnictogens
can
sometimes
be
challenging,
but
aspects
metal-pnictogen
reactivity
are
key.
connecting
comes
from
metal-catalyzed
transformations
such
as
dehydrocoupling
and
hydrofunctionalization.
Pivotal
mechanistic
insights
E-N
heterodehydrocoupling
have
informed
development
highly
active
catalysts
for
these
reactions.
Metal-amido
nucleophilicity
often
at
core
this
reactivity,
which
diverges
phosphine
arsine
dehydrocoupling.
Nucleophilicity
connects
to
earliest
understanding
hydrophosphination
catalysis,
more
recent
leveraging
enhanced
insertion
activity
through
photolysis.
This
photocatalysis
extends
hydroarsination,
may
also
metal-arsenido
than
anticipated.
However,
arsinidene
foreshadowed
related
phosphinidene
by
years.
shows
potential
greater
influence
individual
discoveries
leverage
new
advances
elements,
it
suggests
that
heavier
on
what
possible
with
lighter
elements.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Окт. 5, 2024
P-stereogenic
phosphorus
compounds
are
essential
across
various
fields,
yet
their
synthesis
via
enantioselective
P-C
bond
formation
remains
both
challenging
and
underdeveloped.
We
report
the
first
copper-catalyzed
hydrophosphorylation
of
alkynes,
facilitated
by
a
newly
designed
chiral
1,2-diamine
ligand.
Unlike
previous
methods
that
rely
on
kinetic
resolution
with
less
than
50
%
conversion,
our
approach
employs
distinct
dynamic
asymmetric
transformation
mechanism,
achieving
complete
conversion
racemic
starting
materials.
This
reaction
is
compatible
broad
range
aromatic
aliphatic
terminal
producing
products
high
yields
(up
to
95
%),
exclusive
cis
selectivity,
exceptional
regio-
enantioselectivity
(>20
:
1
r.r.
up
96
ee).
The
resulting
were
further
transformed
into
diverse
array
enantioenriched
scaffolds.
Preliminary
mechanistic
studies
conducted
elucidate
details.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(7)
Опубликована: Дек. 22, 2023
Abstract
This
paper
presents
a
Mn(I)‐catalysed
methodology
for
the
enantioselective
hydrophosphination
of
terminal
alkenyl
aza‐heteroarenes.
The
catalyst
operates
through
H−P
bond
activation,
enabling
successful
diverse
range
alkenyl‐heteroarenes
with
high
enantioselectivity.
presented
protocol
addresses
inherently
low
reactivity
and
commonly
encountered
suboptimal
enantioselectivities
these
challenging
substrates.
As
an
important
application
we
show
that
this
method
facilitates
synthesis
non‐symmetric
tridentate
P,N,P‐containing
ligand
like
structure
in
just
two
synthetic
steps
using
single
catalytic
system.
Abstract
Hydrophosphination
and
oxyphosphination
are
two
important
topical
reactions
in
order
to
prepare
organophosphorus
derivatives
from
unsaturated
such
as
alkenes
alkynes
a
more
sustainable
fashion.
Noticeably,
metal
catalysed
versions
have
shown
great
interest
efficiency.
By
contrast,
the
use
of
earth
abundant
transition
based
catalysts
for
transformations
is
less
reported,
even
if
there
growing
during
last
decade.
This
review
article
reports
highlights
recent
developments
using
manganese,
iron,
cobalt,
nickel
copper
hydro‐
oxyphosphination,
notably
exhibiting
selectivity,
functional
group
tolerance,
milder
conditions
catalyst
design.
Even
significant
progresses
were
made,
scopes
still
rather
limited
(mainly
focused
on
activated
olefins
styrenes)
chemo‐
stereo‐selectivity
issues
be
solved,
asymmetric
transformations.
Of
interest,
visible
light
including
blue
one
activator
emerged,
giving
promising
stimulating
results
at
ambient
conditions.