Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(13)
Опубликована: Янв. 25, 2022
Herein,
a
copper(I)-catalyzed
reaction
of
diarylphosphines
and
O-benzoyl
hydroxylamines
is
developed.
In
the
cases
symmetrical
diarylphosphines,
series
aminophosphinites
prepared
in
high
yields.
unsymmetrical
an
array
P-chiral
synthesized
yields
with
enantioselectivity
by
using
copper(I)-(R,RP
)-Ph-FOXAP
complex
as
chiral
catalyst.
Based
on
several
control
experiments
31
P
NMR
studies,
two-electron
redox
mechanism
involving
dynamic
kinetic
asymmetric
transformation
proposed
for
reaction.
Finally,
one
representative
phosphoric
amide
generated
through
oxidation
H2
O2
transformed
to
diarylphosphinate
yield
retained
enantioselectivity,
which
allows
further
transformations
towards
various
tertiary
phosphines.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(52), С. 27241 - 27246
Опубликована: Ноя. 5, 2021
The
catalytic
asymmetric
synthesis
of
P-chiral
phosphorus
compounds
is
an
important
way
to
construct
ligands.
Herein,
we
report
a
new
strategy
that
adopts
the
pyridinyl
moiety
as
coordinating
group
in
cobalt-catalysed
nucleophilic
addition/alkylation
secondary
phosphine
oxides.
A
series
tertiary
oxides
were
generated
with
up
99
%
yield
and
99.5
ee,
broad
functional-group
tolerance.
Mechanistic
studies
reveal
(R)-secondary
preferentially
interact
cobalt
catalysts
produce
P-stereogenic
compounds.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(52), С. 27288 - 27292
Опубликована: Сен. 28, 2021
Abstract
A
Pd‐catalyzed
hydrophosphinylation
of
alkyl
and
aryl‐oxyallenes
with
phosphine
oxides
has
been
developed
for
the
efficient
rapid
construction
a
family
chiral
allylic
diverse
range
functional
groups.
This
methodology
was
further
applied
in
facile
2
H
‐chromene
later
stage
functionalization
cholesterol.
Angewandte Chemie International Edition,
Год журнала:
2021,
Номер
60(52), С. 27247 - 27252
Опубликована: Окт. 21, 2021
P-stereogenic
tert-
and
sec-phosphines
have
wide
applications
in
asymmetric
catalysis,
materials,
pharmaceutical
chemistry,
however,
their
practical
synthesis
still
constitutes
a
significant
challenge.
Herein,
successful
kinetic
resolution
of
rac-secondary
phosphine
oxides
via
the
enantioselective
P-benzylation
process
catalyzed
by
palladium/Xiao-Phos
was
designed.
Both
sec-phosphine
were
delivered
good
yield
excellent
enantiopurity
(selectivity
factor
up
to
226.1).
The
appealing
synthetic
utilities
are
further
demonstrated
facile
preparation
several
valuable
P-chiral
compounds,
precursors
bidentate
ligands,
as
well
transition
metal
complexes.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(28), С. 12619 - 12626
Опубликована: Июль 8, 2022
Chiral
organophosphorous
compounds
are
very
important
in
catalysis,
organic
syntheses,
and
medicinal
chemistry.
However,
catalytic
enantioselective
protocols
for
the
axially
chiral
allenyl
phosphorus
have
never
been
reported.
Herein,
a
palladium-catalyzed
carbon–phosphorus
bond
formation
reaction
affording
phosphonates
has
developed.
The
enjoys
high
yields
ees
accommodating
wide
range
of
functional
groups.
Mechanistic
studies
unveiled
an
overwhelming
kinetic
resolution
process.
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(7), С. 2893 - 2898
Опубликована: Фев. 14, 2022
Transition-metal-catalyzed
branched
and
enantioselective
allylic
substitution
of
monosubstituted
precursors
with
carbon,
nitrogen,
oxygen,
sulfur,
fluoride
nucleophiles
has
been
well-established.
However,
such
a
selective
carbon–phosphorus
bond
formation
not
realized
probably
due
to
the
catalyst
deactivation
by
strong
coordinating
nature
phosphinylating
reagents.
Herein,
we
report
Rh-catalyzed
highly
regio-
synthesis
phosphine
oxides
in
presence
chiral
bisoxazoline-phosphine
ligand.
The
application
α-hydroxylalkylphosphine
keep
low
concentration
secondary
is
essential
for
high
yields.
addition
diphenyl
phosphoric
acid
was
found
only
activate
alcohols
but
also
accelerate
formation.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(24)
Опубликована: Март 29, 2022
Abstract
A
copper‐catalyzed
asymmetric
aryl
C−P
cross‐coupling/cyclization
reaction
was
successfully
developed
via
dynamic
kinetic
transformation
(DYKAT)
under
mild
conditions.
This
study
provides
a
general
and
simple
method
for
the
catalytic
enantioselective
synthesis
of
stable
six‐,
seven‐
eight‐membered
P‐stereogenic
phosphorus
heterocycles
with
excellent
enantioselectivities
moderate
to
high
yields.
One‐pot
gram‐scale
P‐heterocycle
from
commercially
available
materials
also
accomplished
enantioselectivity
yield.
Organic Letters,
Год журнала:
2022,
Номер
24(5), С. 1258 - 1262
Опубликована: Фев. 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.
Coordination Chemistry Reviews,
Год журнала:
2023,
Номер
489, С. 215192 - 215192
Опубликована: Май 9, 2023
Since
the
development
of
BisP*
ligand
by
Imamoto,
P-stereogenic
phosphines
bearing
a
bulky
tert-butyl
group
and
smaller
alkyl
have
demonstrated
extraordinary
proficiency
in
wide
range
asymmetric
processes.
Over
time,
this
class
ligands
has
brought
about
introduction
more
rigid
backbones,
three-hindered
quadrant
concept,
substitution
adamantyl.
The
methyl
fragment
also
been
introduced
phosphino-oxazoline-type
ligands,
chemists
industrial
sector
contributed
to
evolution
reporting
first
successful
Buchwald-type
monophosphines
for
coupling
reactions.
present
review
covers
synthesis
applications
that
developed
since
advent
late
1990s,
with
special
emphasis
on
successfully
applied
catalysis.
