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(26)
Опубликована: Апрель 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,
Год журнала:
2023,
Номер
62(16)
Опубликована: Фев. 22, 2023
A
chiral
Brønsted
acid-catalysed
asymmetric
hydrophosphinylation
of
2-vinylazaarenes
by
secondary
phosphine
oxides
is
described.
variety
P-chiral
2-azaaryl-ethylphosphine
are
synthesized
with
high
yields
and
ees,
which
both
the
substituents
phosphines
azaarenes
can
be
flexibly
modulated,
underscoring
an
exceptionally
broad
scope
substrates.
These
adducts
valuable
to
metal
catalysis
since
resultant
tertiary
from
reduction
them
verified
as
a
kind
effective
C1
-symmetric
1,5-hybrid
P,N-ligands.
Importantly,
this
platform
enables
generic
efficient
kinetic
resolution
oxides.
It
thus
provides
expedient
approach
access
enantiomers
derived
hydrophosphinylation,
further
improving
utility
method.
Chemical Science,
Год журнала:
2023,
Номер
14(16), С. 4413 - 4417
Опубликована: Янв. 1, 2023
An
enantioselective
hydrophosphination
of
alkenyl
isoquinolines
is
developed
by
using
a
copper-chiral
diphosphine
ligand
catalyst.
It
provides
direct
and
atom-efficient
approach
to
prepare
variety
chiral
phosphines
with
an
isoquinoline
unit
in
good
yields
high
enantioselectivities.
In
addition,
these
phosphine
products
are
useful
bidentate
P,N-ligands
which
showed
potential
application
asymmetric
catalysis.
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
