Asian Journal of Organic Chemistry,
Год журнала:
2024,
Номер
13(11)
Опубликована: Авг. 16, 2024
Abstract
Visible‐light‐driven
dual
catalysis
was
employed
to
stereoselectively
produce
densely
substituted
cyclobutanes
from
Erlenmeyer‐Plöchl
azlactones.
The
single‐step
preparation
of
non‐natural
amino
acid
dimers
containing
the
cyclobutane
moiety
achieved
through
a
synergy
between
iridium
photocatalysis
and
catalytic
nickel(II)
triflate
as
Lewis
acid.
desired
1,2‐(
zeta
)‐
Z
,
E
‐isomers
were
isolated
in
good
yields
with
high
regio‐
diastereoselectivity
(in
all
cases,
>19
:
1
d.r.).
To
best
our
knowledge,
this
is
first
report
direct
access
truxinic
analogues
using
Control
experiments,
EPR
reaction
monitoring,
DFT
calculations
suggest
that
presence
acid,
combined
use
powerful
blue
LEDs,
plays
crucial
role
reactivity
reaction.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(24)
Опубликована: Апрель 11, 2024
Abstract
We
report
a
family
of
donor‐acceptor
thermally
activated
delayed
fluorescent
(TADF)
compounds
based
on
derivatives
DMAC‐TRZ
,
that
are
strongly
photoreducing.
Both
E
ox
and
thus
*
could
be
tuned
via
substitution
the
DMAC
donor
with
Hammett
series
p
‐substituted
phenyl
moieties
while
red
remained
effectively
constant.
These
were
assessed
in
photoinduced
dehalogenation
aryl
halides,
analogues
bearing
electron
withdrawing
groups
found
to
produce
highest
yields.
Substrates
up
=−2.72
V
dehalogenated
at
low
PC
loading
(1
mol
%)
under
air,
conditions
much
milder
than
previously
reported
for
this
reaction.
Spectroscopic
chemical
studies
demonstrate
all
PCs,
including
literature
reference
photodegrade,
it
is
these
photodegradation
products
responsible
reactivity.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(41)
Опубликована: Июль 5, 2024
Abstract
Cyclic
amino(alkyl)
and
cyclic
amino(aryl)
carbenes
(cAACs/cAArCs)
have
been
established
as
very
useful
ligands
for
catalytic
photonic
applications
of
transition
metal
complexes.
Herein,
we
describe
the
synthesis
a
structurally
related
sterically
demanding,
electrophilic
[2.2]isoindolinophanyl‐based
carbene
(iPC)
that
bears
[2.2]paracyclophane
moiety.
The
latter
leads
to
more
delocalized
frontier
orbitals
intense
green
fluorescence
(HiPC)OTf
(
2
)
from
an
intra‐ligand
charge
transfer
1
ILCT)
state
in
solid
state.
Base‐promoted
free
led
unusual
ring
expansion
subsequent
dimerization
reaction,
but
beneficial
ligand
properties
can
be
exploited
by
trapping
situ
at
center.
iPC
is
potent
π‐chromophore,
which
participates
low
energy
metal‐to‐ligand
(ML)CT
transitions
[RhCl(CO)
(iPC)]
4
IL‐“through‐space”‐CT
[Au(iPC)
]OTf
5
).
steric
demand
high
stability
against
air,
moisture,
or
solvent
attack,
ultralong‐lived
phosphorescence
with
lifetime
185
μs
observed
solution.
photophysical
electronic
ligand,
including
large
accessible
π
surface
area,
were
employing
highly
efficient
(EnT)
photocatalysis
[2+2]
styrene
cycloaddition
reaction
using
,
outperformed
other
photocatalysts
comparison.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(41)
Опубликована: Июль 5, 2024
Abstract
Cyclic
amino(alkyl)
and
cyclic
amino(aryl)
carbenes
(cAACs/cAArCs)
have
been
established
as
very
useful
ligands
for
catalytic
photonic
applications
of
transition
metal
complexes.
Herein,
we
describe
the
synthesis
a
structurally
related
sterically
demanding,
electrophilic
[2.2]isoindolinophanyl‐based
carbene
(iPC)
that
bears
[2.2]paracyclophane
moiety.
The
latter
leads
to
more
delocalized
frontier
orbitals
intense
green
fluorescence
(HiPC)OTf
(
2
)
from
an
intra‐ligand
charge
transfer
1
ILCT)
state
in
solid
state.
Base‐promoted
free
led
unusual
ring
expansion
subsequent
dimerization
reaction,
but
beneficial
ligand
properties
can
be
exploited
by
trapping
situ
at
center.
iPC
is
potent
π‐chromophore,
which
participates
low
energy
metal‐to‐ligand
(ML)CT
transitions
[RhCl(CO)
(iPC)]
4
IL‐“through‐space”‐CT
[Au(iPC)
]OTf
5
).
steric
demand
high
stability
against
air,
moisture,
or
solvent
attack,
ultralong‐lived
phosphorescence
with
lifetime
185
μs
observed
solution.
photophysical
electronic
ligand,
including
large
accessible
π
surface
area,
were
employing
highly
efficient
(EnT)
photocatalysis
[2+2]
styrene
cycloaddition
reaction
using
,
outperformed
other
photocatalysts
comparison.
New Journal of Chemistry,
Год журнала:
2024,
Номер
48(30), С. 13261 - 13269
Опубликована: Янв. 1, 2024
Using
Zn-dipyrrins
as
photocatalysts
involves
exciting
an
intramolecular
charge-transfer
(ICT)
state
and
intersystem
crossing
(ISC).
To
optimize
the
catalyst,
studying
ISC
branching
pathways
competing
with
fluorescence
internal
conversion
(IC)
is
essential.
Asian Journal of Organic Chemistry,
Год журнала:
2024,
Номер
13(11)
Опубликована: Авг. 16, 2024
Abstract
Visible‐light‐driven
dual
catalysis
was
employed
to
stereoselectively
produce
densely
substituted
cyclobutanes
from
Erlenmeyer‐Plöchl
azlactones.
The
single‐step
preparation
of
non‐natural
amino
acid
dimers
containing
the
cyclobutane
moiety
achieved
through
a
synergy
between
iridium
photocatalysis
and
catalytic
nickel(II)
triflate
as
Lewis
acid.
desired
1,2‐(
zeta
)‐
Z
,
E
‐isomers
were
isolated
in
good
yields
with
high
regio‐
diastereoselectivity
(in
all
cases,
>19
:
1
d.r.).
To
best
our
knowledge,
this
is
first
report
direct
access
truxinic
analogues
using
Control
experiments,
EPR
reaction
monitoring,
DFT
calculations
suggest
that
presence
acid,
combined
use
powerful
blue
LEDs,
plays
crucial
role
reactivity
reaction.
