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.
combined
experimental
theoretical
mechanistic
study
supports
insertion
Cu(I)-phosphido
intermediate
into
strained
olefin.
Density
functional
theory
calculations
reveal
migratory
as
stereodetermining
step
pathway,
with
final
product
formation
occurring
via
syn-protodemetalation.
Enrichment
phosphorus
stereocenters
is
demonstrated
DyKAT
process.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(26)
Published: April 26, 2023
Transition
metal-catalyzed
hydrofunctionalization
of
methylenecyclopropanes
(MCPs)
has
presented
a
considerable
challenge
due
to
the
difficult
manipulation
regioselectivity
and
complicated
reaction
patterns.
Herein,
we
report
straightforward
Pd-catalyzed
ring-opening
hydrophosphinylation
MCPs
via
highly
selective
C-C
bond
cleavage.
This
method
allows
for
rapid
efficient
access
wide
range
chiral
allylic
phosphine
oxides
in
good
yields
high
enantioselectivities.
Additionally,
density
functional
theory
(DFT)
calculations
were
performed
elucidate
mechanism
origin
enantioselectivity.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(36)
Published: June 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
Advanced Science,
Journal Year:
2024,
Volume and Issue:
11(21)
Published: March 13, 2024
Abstract
Chiral
1,
n‐bis(boronate)
plays
a
crucial
role
in
organic
synthesis
and
medicinal
chemistry.
However,
their
catalytic
asymmetric
has
long
posed
challenge
terms
of
operability
accessibility
from
readily
available
substrates.
The
recent
discovery
the
C═C
bond
formation
through
β‐C
elimination
methylenecyclopropanes
(MCP)
provided
an
exciting
opportunity
to
enhance
molecular
complexity.
In
this
study,
catalyzed
cascade
hydroboration
MCP
is
developed.
By
employing
different
ligands,
various
homoallylic
boronate
intermediate
are
obtained
ring
opening
process.
Subsequently,
with
HBpin
or
B
2
pin
resulted
enantioenriched
chiral
1,3‐
1,4‐bis(boronates)
high
yields,
accompanied
by
excellent
chemo‐
enantioselectivities.
selective
transformation
these
two
distinct
C─B
bonds
also
demonstrated
application
potential
synthesis.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
Although
enantioselective
hydrofunctionalizations
of
nitrones
are
established
for
synthesis
various
types
chiral
hydroxylamines,
the
asymmetric
catalytic
hydrophosphinylation
remains
highly
challenging.
Herein,
an
efficient
of...
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(7)
Published: Dec. 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.
ChemCatChem,
Journal Year:
2024,
Volume and Issue:
unknown
Published: May 27, 2024
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.
