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.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(17)
Published: Feb. 15, 2024
Abstract
A
general
approach
to
the
direct
deoxygenative
transformation
of
primary,
secondary,
and
tertiary
alcohols
has
been
developed.
It
undergoes
through
phosphoranyl
radical
intermediates
generated
by
addition
exogenous
iodine
trivalent
alkoxylphosphanes.
Since
these
alkoxylphosphanes
are
readily
in
situ
obtained
from
commercially
available,
inexpensive
chlorodiphenylphosphine,
a
diverse
range
with
various
functional
groups
can
be
utilized
proceed
cross‐couplings
alkenes
or
aryl
iodides.
The
selective
polyhydroxy
substrates
rapid
synthesis
complex
organic
molecules
also
demonstrated
this
method.
The
excitation
of
carbonyl
compounds
by
light
to
generate
radical
intermediates
is
a
distinctive
mode
molecular
activation.
These
processes
play
important
roles
in
organic
synthesis,
especially
for
the
challenging
formation
carbon-carbon
bonds
that
conventional
two-electron
chemical
are
unable
achieve.
This
approach
has
historically
been
restricted
ketones
and
aldehydes,
carboxylic
acids
have
overlooked
due
high
energy
requirements
their
low
quantum
efficiency.
development
robust
general
method
direct
acid
derivatives
holds
significant
promise
advancing
field
chemistry.
A
successful
activation
strategy
necessitates
bathochromic
shift
absorbance
profile,
an
increase
triplet
diradical
lifetime,
ease
further
functionalization.
We
present
phosphorus-based
through
single-flask
transformation
into
acyl
phosphonates
access
synthetically
useful
diradicals
under
visible
or
near-ultraviolet
irradiation.
use
phosphorus
circumvents
unproductive
Norrish
type
I
processes,
promoting
selectivity
enables
new
hydrogen
atom
transfer
(HAT)
logic
facilitates
diverse
reactivity.
Employing
this
promotes
efficient
scaffold
remodeling
various
annulation,
contraction,
expansion
manifolds.
HAT
enabled
easily
accessed
represents
potential
pharmaceuticals,
materials
science,
environmental
applications.
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.
