Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(23)
Published: April 4, 2024
Abstract
The
present
study
reports
an
unprecedented
protocol
for
the
phosphonylation
of
unactivated
C(sp
3
)−H
bonds.
By
utilizing
1
mol
%
4DPAIPN
(1,2,3,5‐tetrakis(diphenylamino)‐4,6‐dicyanobenzene)
as
catalyst,
satisfactory
yields
γ‐phosphonylated
amides
are
obtained
through
a
visible‐light‐induced
reaction
between
N
‐((4‐cyanobenzoyl)oxy)alkanamides
and
9‐fluorenyl
o
‐phenylene
phosphite
at
room
temperature.
This
demonstrates
broad
substrate
scope
wide
functional
group
compatibility.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(15), P. 3208 - 3212
Published: April 10, 2024
Herein,
we
report
a
catalyst-free
reaction
of
cyclobutanone
oximes
with
chlorophosphines
(R2PCl),
which
forms
fragile
C═N–O–PR2
species
that
undergoes
N–O
homolysis,
fragmentation,
and
radical–radical
coupling,
leading
to
the
formation
cyano-containing
phosphine
oxides
in
good
yields.
The
features
an
situ
activation
for
radical
generation,
R2PCl
plays
dual
role
as
both
activator
reactant.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: May 1, 2025
A
visible
light-induced
decarboxylative
radical
coupling
between
N-hydroxyphthalimide
esters
and
phosphonites
or
phosphinites
has
been
developed.
The
corresponding
phosphinates
phosphine
oxides
could
be
obtained
under
mild
conditions.
No
transition
metals
toxic
reagents
were
involved.
This
method
provides
a
low-cost
practical
alternative
for
synthesizing
functionalized
oxides.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(9)
Published: Jan. 29, 2024
Abstract
This
review
discusses
various
methods
for
the
preparation
of
air
and
water‐stable
organozinc
pivalates
containing
aryl,
heteroaryl,
alkyl,
alkenyl,
benzyl
alkynyl
scaffolds
achieved
via
i)
selective
metalation
(DoM)
in
presence
a
directing
group
(DG)
aromatic
core,
ii)
direct
oxidative
Zn
metal
insertion/or
X/M
exchange
reaction
followed
by
transmetalation
with
Zn(Opiv)
2
,
which
are
then
further
functionalized
Negishi
cross‐coupling
reactions,
or
trapping
different
electrophiles
used
transition
catalysts
(Pd,
Co,
Ni,
Cu).
Selective
deprotonation
aryl
heteroaryl
derivatives
can
be
performed
using
LDA,
TMP−Mg
TMP−Zn
reagents
on
system.
Different
based
non‐aromatic
structures
electron‐rich
electron‐deficient
substituents
undergo
metal‐catalyzed
C(sp
)−C(sp
),
)−C(sp)
3
)
types
reactions
halides
diaryl
disulfides
under
mild
conditions
sustainable
catalytic
process.
The
literature
report
shows
that
polyfunctionalized
nitrogen,
oxygen
sulfur‐based
bioactive
pharmaceutical
scaffolds,
natural
products
target
organic
molecules
accessible
highly
moisture‐stable
coupling
conditions.
Importantly,
sensitive
functional
groups
tolerable,
commercially
available
substrates
inexpensive
low
toxic
employed
pivalates.
In
this
context,
article
provides
detailed
summary
numerous
synthetic
strategies
practical
isolated
pure
solid
form.
Additionally,
some
recently
published
examples
demonstrating
their
application
synthesis
discussed.
Advanced Agrochem,
Journal Year:
2024,
Volume and Issue:
4(1), P. 13 - 29
Published: July 27, 2024
Organophosphate
analogues
are
commonly
occurring
structural
features
that
widely
present
in
numerous
natural
substances,
biologically
active
molecules
and
modern
pharmaceutical
compounds.
The
development
of
efficient
strategies
for
the
preparation
these
is
still
attractive
but
challenging
organophosphorus
chemistry.
In
order
to
fill
this
gap,
different
new
routes
have
been
discovered
including
direct
phosphonylation
alkyl
radicals,
indirect
Arbuzov
radicals
nucleopilic
phosphorus.
short
review,
we
attempted
summarize
recent
developments
synthesis
phosphonates
facilitate
green
pharmacological
by
emphasizing
their
variety
products,
specificity
relevance,
providing
underlying
mechanistic
rationale
whenever
it
possible.
We
aim
provide
readers
with
a
comprehensive
understanding
current
state
field
contribute
future
research.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(8)
Published: Jan. 5, 2024
Abstract
Reported
herein
is
an
unprecedented
protocol
for
C(sp
3
)‐phosphinylation.
With
1
mol
%
4CzIPN
(1,2,3,5‐tetrakis(carbazol‐9‐yl)‐4,6‐dicyanobenzene)
as
the
catalyst,
visible
light
induced
reaction
of
redox‐active
esters
aliphatic
carboxylic
acids
with
dimethyl
arylphosphonites
or
diethyl
alkylphosphonites
at
room
temperature
provides
corresponding
decarboxylative
phosphinylation
products
in
satisfactory
yields.
The
exhibits
broad
substrate
scope
and
wide
functional‐group
compatibility,
enabling
late‐stage
modification
complex
molecules
rapid
synthesis
bioactive
phosphinic
such
glutamine
synthetase
phosphinothricin
a
kynureninase
inhibitor.
A
radical‐polar
crossover
mechanism
involving
formation
subsequent
oxidation
phosphoranyl
radicals
followed
by
nucleophilic
demethylation
(or
deethylation)
proposed.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(16), P. 4502 - 4507
Published: Jan. 1, 2024
A
photoinduced
formal
deformylative
phosphonylation
utilizing
easily
available
aldehydes
was
established,
providing
a
practical
synthetic
route
to
alkylphosphonates
from
aliphatic
aldehydes.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 19, 2024
C–P
bond
formation
has
typically
been
achieved
by
a
single-electron
transfer
process.
Herein,
novel
class
of
oxime
ester
bifunctionalization
reagents
were
first
applied
to
the
photocatalytic
β-aminophosphorylation
modular
olefins.
The
bifunctional
generate
two
distinct
radical
species
(imine
and
phosphoryl
radicals)
that
exhibit
excellent
regioselectivity.
Subsequently,
these
radicals
are
attached
olefins
through
single-step
EnT
catalytic
process,
establishing
synthetic
pathway.
This
protocol
is
characterized
regioselectivity,
broad
functional
group
tolerance,
mild
reaction
conditions,
which
would
enrich
diversity
versatility
facilitate
diversity-oriented
synthesis
β-aminophosphorylated
complex
molecule
scaffolds.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(50), P. 9014 - 9019
Published: Dec. 8, 2023
Photoinduced
generation
of
phosphoranyl
radicals
offers
a
versatile
strategy
to
access
variety
synthetically
valuable
radicals.
A
long-standing
challenge
remains
in
the
regulation
radical
undergo
α-scission
pathway,
although
β-scission
mode
has
been
intensively
studied.
We
herein
developed
an
unprecedented
protocol
for
selective
P(OH)R3
intermediate
under
photocatalytic
conditions.
This
efficient
P-C
bond
cleavage
via
successfully
utilized
alkylation/fluoroalkylation
alkenes.
