Angewandte Chemie,
Journal Year:
2022,
Volume and Issue:
135(4)
Published: Nov. 22, 2022
Abstract
A
chiral
Brønsted
acid
catalysed
phosphine‐mediated
deoxygenation
protocol
is
reported.
This
metal‐free
method
provides
a
precise
kinetic
resolution
platform
for
azaarylethynyl
tertiary
alcohols,
which
are
broad
category
of
biologically
and
synthetically
important
azaarene
derivatives.
In
addition
to
providing
an
efficient
the
first
asymmetric
preparation
these
strategy
facilitates
construction
azaaryl‐functionalized
allenes
with
good
excellent
enantioselectivities.
The
high
selectivity
factors
(
s
up
235),
substrate
scope,
ability
convert
azaaryl
compounds
into
both
alcohols
robustly
underscore
efficiency
promising
utility
this
method.
practicability
further
validated
by
successful
synthesis
deuterated
ee
values
substantial
incorporation
deuterium
using
inexpensive
D
2
O
as
source.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(52), P. 27288 - 27292
Published: Sept. 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,
Journal Year:
2022,
Volume and Issue:
62(3)
Published: Nov. 25, 2022
Abstract
A
Cu/CPA
co‐catalytic
system
has
been
developed
for
achieving
the
direct
hydrophosphinylation
of
alkynes
with
phosphine
oxides
in
delivering
novel
axially
chiral
phosphorus‐containing
alkenes
high
yields
and
excellent
enantioselectivities
(up
to
99
%
yield
ee).
DFT
calculations
were
performed
elucidate
reaction
pathway
origin
enantiocontrol.
This
streamlined
modular
methodology
establishes
a
new
platform
design
application
styrene‐phosphine
ligands.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(16)
Published: Feb. 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.
Chemistry - A European Journal,
Journal Year:
2021,
Volume and Issue:
27(42), P. 10807 - 10825
Published: May 25, 2021
The
renaissance
of
Brønsted
superbases
is
primarily
based
on
their
pronounced
capacity
for
a
large
variety
chemical
transformations
under
mild
reaction
conditions.
Four
major
set
screws
are
available
the
selective
tuning
basicity:
nature
basic
center
(N,
P,
…),
degree
electron
donation
by
substituents
to
central
atom,
possibility
charge
delocalization,
and
energy
gain
hydrogen
bonding.
Within
past
decades,
plethora
neutral
electron-rich
phosphine
phosphazene
bases
have
appeared
in
literature.
Their
outstanding
properties
advantages
over
inorganic
or
charged
now
made
them
indispensable
as
auxiliary
deprotonation
processes.
Herein,
an
update
chemistry
phosphines
phosphazenes
given.
In
addition,
due
widespread
interest,
use
catalysis
ligands
coordination
highlighted.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(4)
Published: Nov. 22, 2022
A
chiral
Brønsted
acid
catalysed
phosphine-mediated
deoxygenation
protocol
is
reported.
This
metal-free
method
provides
a
precise
kinetic
resolution
platform
for
azaarylethynyl
tertiary
alcohols,
which
are
broad
category
of
biologically
and
synthetically
important
azaarene
derivatives.
In
addition
to
providing
an
efficient
the
first
asymmetric
preparation
these
strategy
facilitates
construction
azaaryl-functionalized
allenes
with
good
excellent
enantioselectivities.
The
high
selectivity
factors
(s
up
235),
substrate
scope,
ability
convert
azaaryl
compounds
into
both
alcohols
robustly
underscore
efficiency
promising
utility
this
method.
practicability
further
validated
by
successful
synthesis
deuterated
ee
values
substantial
incorporation
deuterium
using
inexpensive
D2
O
as
source.
Angewandte Chemie,
Journal Year:
2021,
Volume and Issue:
133(52), P. 27494 - 27498
Published: Sept. 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.
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
28(42)
Published: May 11, 2022
The
formal
enantioselective
umpolung
addition
of
dialkyl
phosphites
to
2-azaaryl
ketones
was
developed
under
Brønsted
base
catalysis.
reaction
involves
the
protonation
transient
α-oxygenated
(2-azaaryl)methyl
anion
generated
through
1,2-addition
phosphite
ketone
and
subsequent
[1,2]-phospha-Brook
rearrangement.
A
chiral
bis(guanidino)iminophosphorane
organosuperbase
efficiently
catalyzed
provide
enantio-enriched
phosphates
in
high
yields
with
good
enantioselectivities.
This
is
a
rare
example
catalytic
carbanions
other
than
enolates,
constructing
trisubstituted
stereogenic
center
α
2-azaarenes.
Chemistry - An Asian Journal,
Journal Year:
2022,
Volume and Issue:
17(11)
Published: April 12, 2022
A
highly
efficient
asymmetric
Michael
addition
of
bulky
glycine
imine
to
α,β-unsaturated
isoxazoles
has
been
achieved
by
using
5
mol%
chiral
cyclopropenimine
as
a
organo-superbase
catalyst
under
mild
conditions.
adducts
were
obtained
in
excellent
yields
(up
97%)
and
stereoselectivities
>99
:
1
dr
98%
ee).
significant
solvent
effect
was
found
these
organosuperbase
catalyzed
reactions.
Gram-scale
preparation
their
transformations
are
realized
provide
corresponding
products
without
loss
stereoselectivities.
The
configurations
adduct
determined
single-crystal
X-ray
diffraction
analysis.
Angewandte Chemie,
Journal Year:
2023,
Volume and Issue:
135(16)
Published: Feb. 22, 2023
Abstract
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
C
1
‐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.
Chemistry - An Asian Journal,
Journal Year:
2022,
Volume and Issue:
17(24)
Published: Oct. 20, 2022
The
organocatalytic
enantioselective
hydrophosphinylation
of
various
secondary
phosphine
sulfides
with
aromatic
and
aliphatic
nitroalkenes
is
presented
in
this
study.
reaction
produced
chiral
β-nitrophosphine
excellent
yields
enantioselectivities
(up
to
99%
yield
ee).
Furthermore,
the
can
be
easily
converted
into
α-substituted
β-aminophosphine,
which
a
family
useful
P,
N-ligands
catalysts.
