European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
27(4)
Published: Dec. 5, 2023
Abstract
The
synthesis
of
P‐stereogenic
phosphorus
compounds
has
gained
considerable
attention
due
to
their
wide
applications
across
many
research
fields.
Among
the
available
strategies,
transition
metal‐catalyzed
asymmetric
transformation
pentavalent
phosphoryl
(H−P(O))
precursors
is
particularly
appealing.
This
approach
involves
a
direct
C−P
bond‐forming
process,
rendering
it
straightforward,
and
employs
readily
available,
bench‐stable
H−P(O)
reagents
that
are
compatible
with
various
metal
catalysts.
Recent
years
have
witnessed
significant
progress
in
this
field,
primary
focus
on
cross‐couplings
hydrophosphorylations.
Concept
article
provides
brief
summary
recent
progress,
highlights
existing
challenges,
discusses
future
directions
exciting
area.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(5), P. 1258 - 1262
Published: Feb. 2, 2022
A
nickel-catalyzed
benzylic
substitution
of
secondary
phosphine
oxide
was
described,
affording
the
dialkylated
P-stereogenic
tertiary
oxides
with
high
to
excellent
enantioselectivities.
The
reaction
performed
under
mild
conditions
commercially
available
benzyl
chlorides
and
bench
stable
oxides,
exhibiting
broad
functional
group
tolerance.
It
represented
a
practical
example
for
preparation
compounds.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(25)
Published: April 14, 2023
Abstract
Transition‐metal‐catalyzed
enantioselective
P−C
cross‐coupling
of
secondary
phosphine
oxides
(SPOs)
is
an
attractive
method
for
synthesizing
P
‐stereogenic
phosphorus
compounds,
but
the
development
such
a
dynamic
kinetic
asymmetric
process
remains
considerable
challenge.
Here
we
report
unprecedented
highly
intermolecular
coupling
SPOs
and
aryl
iodides
catalyzed
by
copper
complexes
ligated
finely
modified
chiral
1,2‐diamine
ligand.
The
reaction
tolerates
wide
range
iodides,
affording
tertiary
(TPOs)
in
high
yields
with
good
enantioselectivity
(average
89.2
%
ee).
resulting
enantioenriched
TPOs
were
transformed
into
structurally
diverse
‐chiral
scaffolds,
which
are
valuable
as
ligands
catalysts
synthesis.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(15)
Published: Feb. 14, 2023
Abstract
A
general
and
mild
nickel‐catalyzed
enantioselective
C(sp
2
)−P
cross‐coupling
for
synthesizing
P‐stereogenic
phosphine
oxides
has
been
developed.
The
asymmetric
alkenylation/arylation
of
racemic
secondary
with
alkenyl/aryl
bromides
generated
high
yields
enantioselectivities.
Various
functional
groups
were
tolerated,
the
applications
this
method
demonstrated
through
late‐stage
functionalization
product
transformations.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(10), P. 6994 - 7001
Published: May 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,
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
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 19, 2025
Chiral
phosphoramidates
characterized
by
at
least
a
P–N
bond
without
P–C
demonstrate
significant
applicative
value
within
nucleoside
phosphoramidate
prodrugs.
Despite
the
availability
of
methodologies
for
selective
construction
diverse
chiral
organophosphorus
entities,
achieving
P-stereocenters
solely
substituted
heteroatoms
often
relies
on
diastereomeric
synthesis.
Here,
we
present
catalytic
enantioselective
desymmetrization
strategy
using
an
electrophilic
phosphorus
reagent
with
three
leaving
groups
as
substrate,
enabling
three-phase
nucleophilic
attack
various
alcohols
and
amines.
By
generating
broad
range
possible
substituent
combinations
around
atoms,
this
synthetic
may
expedite
synthesis
screening
biologically
active
phosphoramidates.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(5), P. 1286 - 1290
Published: Jan. 1, 2023
Due
to
the
high
reactivity
of
triple
bond,
P-stereogenic
alkynylphosphines
could
be
easily
derivatized,
serving
as
universal
building
blocks
for
structurally
diverse
phosphine
compounds.
However,
synthesis
via
direct
P-C
bond
formation
was
unprecedented.
Here,
we
report
an
efficient
method
with
enantioselectivity
a
Ni-catalyzed
asymmetric
cross-coupling
reaction.
The
reaction
tolerate
variety
functional
groups,
affording
products
that
can
converted
into
useful
derivatives.
