Chemistry - A European Journal,
Год журнала:
2023,
Номер
30(13)
Опубликована: Дек. 23, 2023
The
formation
of
a
five-
or
six-membered
ring
is
known
to
stabilize
unstable
molecular
structures
such
as
hemiacetals.
This
idea
can
also
be
extended
other
high-coordinated
p-block
element
species.
Herein,
we
synthesized
two
novel
polycyclic
organophosphorus
heterocycles
via
Staudinger-type
annulations.
Reactions
either
ortho-phosphinoarenesulfonyl
fluorides
1
ortho-phosphinobenzoic
acid
methyl
esters
4
with
ortho-azidophenols
2
gave
rise
penta-coordinated
P(V)
heterocycles,
benzo-benzo-1,2,3-thiazaphospholo-1,3,2-oxazaphosphole
(B-B-TAP-OAP)
3
and
benzo-benzo-1,2-azaphospholo-1,3,2-oxazaphosphol-12-one
(B-B-AP-OAP)
5
in
satisfactory
yields.
It
remarkable
that
are
both
bench-stable
exhibit
considerable
stability
10
%
aqueous
tetrahydrofuran
solution.
Preliminary
computational
studies
disclosed
the
nitrogen
gas
key
driving
force
for
In
addition,
strong
Si-F
bond
another
contributor
annulation
2.
Chemical Communications,
Год журнала:
2024,
Номер
60(53), С. 6745 - 6748
Опубликована: Янв. 1, 2024
The
cooperation
between
a
geometrically
constrained,
highly
electrophilic
phosphorus(V)
center,
and
an
electronically
rich
tetradentate
bis(amidophenolate)
ligand
enables
the
cleavage
of
CO
bond
from
typical
aldehydes
ketones
delivering
iminio
phosphoramidate
species.
amphiphilic
nature
these
products,
which
is
demonstrated
through
their
reaction
with
Lewis
acids
bases,
use
as
mild
source
silylium
cations
silanes,
allowing
selective
reductive
coupling
to
ethers
under
catalytic
conditions.
Angewandte Chemie,
Год журнала:
2022,
Номер
135(6)
Опубликована: Дек. 16, 2022
Abstract
Rigidly
planar
polycyclic
phosphacycles
featuring
an
internal
dioxaphosphorane
are
promising
photofunctional
materials.
However,
the
lack
of
efficient
synthetic
methods
resulted
in
limited
structural
diversities
which
significantly
hampered
extensive
study.
Herein,
we
report
a
straightforward
three‐component
synthesis
novel
dioxaphosphorane‐fused
diphosphacycles
with
distinctive
photophysical
properties.
Control
experiments
and
theory
calculations
were
performed
to
account
for
plausible
reaction
mechanism.
We
also
systematically
investigated
structure‐property
relationships
these
unprecedented
platforms
by
combining
(X‐ray
analysis,
optical
redox
properties)
theoretical
computations.
Based
on
their
unique
structure
properties,
fluorescent
switch
pH
sensing
was
revealed
dynamic
ring‐opening/ring‐closing
process.
Chemistry - A European Journal,
Год журнала:
2023,
Номер
30(13)
Опубликована: Дек. 23, 2023
The
formation
of
a
five-
or
six-membered
ring
is
known
to
stabilize
unstable
molecular
structures
such
as
hemiacetals.
This
idea
can
also
be
extended
other
high-coordinated
p-block
element
species.
Herein,
we
synthesized
two
novel
polycyclic
organophosphorus
heterocycles
via
Staudinger-type
annulations.
Reactions
either
ortho-phosphinoarenesulfonyl
fluorides
1
ortho-phosphinobenzoic
acid
methyl
esters
4
with
ortho-azidophenols
2
gave
rise
penta-coordinated
P(V)
heterocycles,
benzo-benzo-1,2,3-thiazaphospholo-1,3,2-oxazaphosphole
(B-B-TAP-OAP)
3
and
benzo-benzo-1,2-azaphospholo-1,3,2-oxazaphosphol-12-one
(B-B-AP-OAP)
5
in
satisfactory
yields.
It
remarkable
that
are
both
bench-stable
exhibit
considerable
stability
10
%
aqueous
tetrahydrofuran
solution.
Preliminary
computational
studies
disclosed
the
nitrogen
gas
key
driving
force
for
In
addition,
strong
Si-F
bond
another
contributor
annulation
2.
