The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 14, 2025
A
novel
regioselective
manganese(III)-mediated
radical
cascade
cyclization
of
N-propargyl
enamides
with
various
H-phosphine
oxides,
H-phosphinates
and
H-phosphonates
was
developed.
Mechanistic
studies
show
that
the
reaction
is
mainly
composed
selective
addition
phosphonyl
to
C≡C
bond
intramolecular
6-endo-trig
vinyl
radical.
Utilizing
this
protocol,
we
successfully
synthesized
a
diverse
range
3-phosphorylpyridines
in
high
efficiency
good
functional
group
compatibility
simple
operation.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 23, 2025
We
report
a
highly
regioselective
1,2-addition
of
P(O)-H
compounds
to
the
in
situ
generated
β,γ-alkynyl-α-ketimine
derived
from
3-alkynyl-3-hydroxyisoindolinones,
which
provided
general
protocol
for
preparation
3,3-disubstituted
isoindolinones
featuring
both
phosphoryl
and
alkynyl
groups
at
quaternary
carbon
center.
The
use
only
2-5
mol
%
an
inexpensive
catalyst
(In(ClO4)3·8H2O
or
Bi(OTf)3)
allowed
smooth
output
desired
products
under
mild
conditions
(25
°C,
0.5-24
h)
with
broad
substrate
scope
(35
examples)
up
>99%
yield.
obtained
could
be
further
elaborated
based
on
alkyne
moiety.
initial
asymmetric
trial
indicated
that
BINOL-derived
CPA
enable
enantioselective
induction
46%
yield
77%
ee.
Phosphorus, sulfur, and silicon and the related elements,
Journal Year:
2023,
Volume and Issue:
198(11), P. 867 - 923
Published: July 20, 2023
Secondary
phosphine
oxides
R2P(O)H
are
a
relatively
stable
tautomeric
form
of
secondary
phosphinous
acids
R2P–OH
that
with
imine/iminium
species,
or
their
donors,
compounds
P(O)–Csp3–N
linkage
(the
phospha-Mannich
reaction).
These
can
be
referred
to
as
(α-aminoalkyl)phosphine
oxides,
(α-phosphinoylalkyl)amines,
P(O),N-acetals.
Compared
P–Csp3–N
linkages
P,N-acetals,
products
reactions
involving
phosphines
R2PH,
the
is
significantly
more
allows
for
many
examples
α-functionalized
P(O),N-acetals
and
α-phosphinoylated
N-heterocycles,
whereas
such
P,N-acetals
rare.
Trivalent
derivatives
halides
R2P–Hal,
esters
R2P–OR'
(phosphinites),
amides
R2P–NR'2
(aminophosphines),
phosphides
R2P–PR'2
(biphosphines)
also
participate
in
Mannich-type
mechanisms
depending
on
reactants.
The
react
(α-alkoxyalkyl)amines
(N,O-acetals)
(α-haloalkyl)amines
(N,Hal-acetals),
respectively,
via
Arbuzov-type
intermediates
rearranged
into
alkyl
(Arbuzov
rearrangement).
Furthermore,
unlike
phosphines,
less
sensitive
oxidation,
imines/iminium
species
generated
not
only
under
conventional
Mannich
conditions,
i.e.,
from
N,E-acetals
(E
=
OH,
O,
N,
halogen,
etc.),
but
also,
example,
by
oxidation
α-C-atom
amines,
alcohols
aldehydes
than
amines.
Organic & Biomolecular Chemistry,
Journal Year:
2023,
Volume and Issue:
21(8), P. 1662 - 1666
Published: Jan. 1, 2023
As
an
efficient
and
green
synthesis
method,
the
electrocatalysis
hydrogen
evolution
coupling
reaction
has
been
widely
used
by
chemists
to
realize
combining
of
two
nucleophiles.
In
this
work,
alternative
method
synthesize
6-phosphorylated
phenanthridines
developed
synergistically
utilizing
Mn
catalysis,
with
moderate
relatively
good
yields
achieved.
Mild
oxidant-free
conditions
make
synthetic
applicable
in
various
settings.
Organic Chemistry Frontiers,
Journal Year:
2022,
Volume and Issue:
9(23), P. 6540 - 6546
Published: Jan. 1, 2022
A
visible-light-induced
stereo-
and
regioselective
phosphorylation
of
enamides
with
phosphine
oxides
under
transition-metal-free
conditions
has
been
disclosed.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 18, 2024
A
regioselective
radical
α,γ-diphosphinylation
of
allylamines
with
secondary
phosphine
oxides
by
photoinduced
cobaloxime
catalysis
is
described.
The
reaction
tolerates
a
wide
range
and
oxides,
affording
α-amino
diphosphine
dioxides
in
moderate
to
good
yields
hydrogen
evolution.
synthesis
new
monoxide
ligands
the
promising
antitumor
activities
products
demonstrate
great
potential
applications
this
approach
drug
discovery.
detailed
mechanism
studies
indicate
that
likely
proceeds
through
dehydrogenative
allylic
phosphinylation
nucleophilic
addition
process.
