Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(7), P. 1530 - 1535
Published: Feb. 14, 2022
A
visible-light-promoted
aerobic
oxyphosphorylation
of
α-diazoesters
and
H-phosphine
oxides
has
been
developed.
Using
air
as
the
oxygen
source,
reaction
proceeded
smoothly
at
room
temperature
under
blue-light
irradiation.
The
α-diazoesters,
molecular
oxygen,
are
conveniently
incorporated
into
a
C-O-P(O)
unit
in
one
step.
preliminary
mechanistic
studies
indicated
that
light-triggered
radical
process
is
involved.
developed
strategy
shows
unrevealed
reactivity
diazo
compounds
with
potential
value
synthetic
applications.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(23), P. 9292 - 9296
Published: Nov. 19, 2021
Two
new
visible-light-mediated
strategies
are
described
starting
from
aryldiazoacetates.
The
first
approach
describes
their
reaction
with
azides
to
afford
the
corresponding
imines,
and
then
aryldiazoketones
produces
alkyl
2-carboxylate-2,3,3-trisubstituted
β-lactams.
second
sulfoxides
sulfoxonium
ylides,
followed
by
produce
5-alkoxy-2,2,4-trisubstituted
furan-3(2H)-ones.
These
protocols
take
advantage
of
photolysis
aryldiazoacetates
photochemically
promoted
Wolff
rearrangement
aryldiazoketones.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(2), P. 829 - 839
Published: Jan. 4, 2021
Density
functional
theory
calculations
were
applied
to
study
four
previously
published
metal-catalyzed
[2,3]-rearrangements
from
onium
ylide
intermediates,
in
pursuit
of
generalizations
about
when,
during
these
types
reactions,
catalysts
dissociate.
Our
results
corroborate
past
studies
where
free-ylide
mechanisms
proposed
be
operative.
Results
on
case
indicate
that
the
origin
metal–catalyst
dissociation
can
attributed
primarily
steric
bulkiness
groups
adjacent
carbene
carbon.
Macromolecules,
Journal Year:
2022,
Volume and Issue:
55(9), P. 3423 - 3429
Published: April 22, 2022
Compared
with
linear
thermoplastic
polymers,
thermoset
polymers
three-dimensional
network
structures
exhibit
improved
solvent
tolerance,
heat
resistance,
and
mechanical
strength.
The
radical-mediated
process
is
widely
used
to
cross-link
the
polymer
chains;
however,
this
requires
high
temperature
(>150
°C)
or
UV
irradiation
generate
highly
energetic
radicals,
unavoidably
leading
undesired
side
reactions
uncontrolled
cross-linking
behavior.
This
work
proposes
achieves
a
carbene-mediated
diazo-based
compounds
by
C–H
activation
an
insertion
mechanism
under
relatively
mild
conditions.
A
simple
route
containing
only
one
two
steps
established
synthesize
three
generations
of
cross-linkers
1G,
2G,
3G.
cross-linker
1G
exhibits
lowest
efficiency
due
self-coupling
carbenes.
After
optimizing
chemical
structure
increasing
numbers
diazo
moieties,
significantly
improves
for
2G
3G
cross-linkers.
These
are
applicable
any
bonds.
They
useful
in
wide
range
applications,
from
adhesion
low
surface
energy
ultrahigh
molecular
weight
polyethylene
(UHMWPE)
modification
co-cross-linking.
versatile,
convenient,
practical
strategy
provides
new
opportunities
modification,
cross-linking,
science.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(49)
Published: Oct. 13, 2022
Abstract
We
describe
a
photo‐induced
reaction
for
the
in
situ
generation
of
highly
reactive
alkyl
diazo
species
from
carbonyl
precursors
via
photo‐excitation
N‐tosylhydrazone
anions.
The
intermediates
undergo
efficient
C−H
insertion
aldehydes,
leading
to
productive
synthesis
aldehydes
and
ketones.
method
is
applicable
iterative
densely
functionalized
compounds
through
sequential
trapping
with
various
aldehydes.
proceeds
without
need
any
catalyst
by
light
irradiation
features
high
functional
group
tolerance.
More
than
70
examples,
some
performed
on
gram‐scale,
demonstrate
broad
applicability
this
sequence
synthesis.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(7), P. 1530 - 1535
Published: Feb. 14, 2022
A
visible-light-promoted
aerobic
oxyphosphorylation
of
α-diazoesters
and
H-phosphine
oxides
has
been
developed.
Using
air
as
the
oxygen
source,
reaction
proceeded
smoothly
at
room
temperature
under
blue-light
irradiation.
The
α-diazoesters,
molecular
oxygen,
are
conveniently
incorporated
into
a
C-O-P(O)
unit
in
one
step.
preliminary
mechanistic
studies
indicated
that
light-triggered
radical
process
is
involved.
developed
strategy
shows
unrevealed
reactivity
diazo
compounds
with
potential
value
synthetic
applications.
