Energy
transfer
catalysis
(EnT)
has
had
a
profound
impact
on
contemporary
organic
synthesis
enabling
the
construction
of
higher
in
energy,
complex
molecules,
via
efficient
access
to
triplet
excited
state.
Despite
this,
intermolecular
reactivity,
and
unique
possibility
several
reaction
pathways
central
diradical
rendered
control
over
outcomes,
an
intractable
challenge.
Extended
chromophores
such
as
non-symmetrical
dienes
have
potential
undergo
2+2
cycloaddition,
4+2
cycloaddition
or
geometric
isomerization,
which,
combination
with
other
mechanistic
considerations
(site-
regioselectivity),
results
chemical
reactions
that
are
challenging
regulate.
Leveraging
spin
density
predictive
tool,
use
core
functionality
can
be
adequately
tuned
potentially
modulate
would
highly
revealing
intimate
links
between
structure
EnT
induced
reactivity.
Herein,
we
utilize
boron
tool
explore
reactivity
under
catalysis,
paying
particular
attention
hybridization
effects
target
Through
site-
regioselective
was
realized
employed
motif
effecting
efficiency.
Reaction
divergence
enable
achieved,
while
counterintuitive
regiodivergence
observed
isomerization
versus
cycloaddition.
The
validated
in-depth
investigation
determining
origin
competing
processes
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(14), С. 10142 - 10149
Опубликована: Март 27, 2024
Saturated
bicyclic
compounds
make
up
a
valuable
class
of
building
blocks
in
the
development
agrochemicals
and
pharmaceuticals.
Here,
we
present
synthesis
borylated
bicyclo[2.1.1]hexanes
via
crossed
[2
+
2]-cycloaddition.
Due
to
presence
C–B
bond,
variety
structures
can
be
easily
prepared
that
are
not
accessible
by
other
methods.
Moreover,
rare
photo-ene
reaction
is
also
disclosed,
allowing
for
diastereoselective
trisubstituted
cyclopentanes.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(5), С. 3416 - 3426
Опубликована: Янв. 24, 2024
A
new
design
concept
for
organic,
strongly
oxidizing
photocatalysts
is
described
based
upon
dicationic
acridinium/carbene
hybrids.
highly
modular
synthesis
of
such
hybrids
presented,
and
the
dications
are
utilized
as
novel,
tailor-made
photoredox
catalysts
in
direct
oxidative
C-N
coupling.
Under
optimized
conditions,
benzene
even
electron-deficient
arenes
can
be
oxidized
coupled
with
a
range
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(25)
Опубликована: Апрель 11, 2024
Abstract
While
polyborylated
alkenes
are
being
recognized
for
their
elevated
status
as
highly
valuable
reagents
in
modern
organic
synthesis,
allowing
efficient
access
to
a
diverse
array
of
transformations,
including
the
formation
C−C
and
C‐heteroatom
bonds,
potential
energy‐transfer
reactive
groups
has
remained
unexplored.
Yet,
this
holds
key
generating
elusive
biradical
species,
which
can
be
captured
by
olefins,
thereby
leading
construction
new
highly‐borylated
scaffolds.
Herein,
we
report
designed
strategy
photosensitized
[2+2]‐cycloadditions
poly‐borylated
with
various
olefins
enabling
regioselective
synthesis
cyclobutane
motifs,
1,1‐di‐,
1,1,2‐tri‐,
1,1,2,2‐tetra‐borylated
cyclobutanes.
In
fact,
these
compounds
belong
family
that
presently
lacks
synthetic
pathways.
Interestingly,
when
α‐methylstyrene
was
used,
reaction
involves
an
interesting
1,5‐hydrogen
atom
transfer
(HAT).
Mechanistic
deuterium‐labeling
studies
have
provided
insight
into
outcome
process.
addition,
cyclobutanes
then
demonstrated
useful
selective
oxidation
processes
resulting
cyclobutanones
γ‐lactones.
Angewandte Chemie International Edition,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 21, 2025
Recently,
in
a
communication
to
this
journal,
Qiao,
Jang,
and
coworkers
described
an
asymmetric
photoredox
reaction
promoted
by
TADF
cyanoarene
photocatalysts
(specifically
4DPAPN
(3,4,5,6-tetrakis(diphenylamino)phthalonitrile)).
The
authors
claimed
that
the
high
reduction
potential
required
for
acetonitrile
was
achieved
radical
anion
of
photocatalyst
its
excited
state,
which
initiated
reaction.
This
mechanism
is
usually
named
consecutive
photoinduced
electron
transfer
(ConPeT),
two
photons
are
involved:
first
one
excite
generate
4DPAPN•-
second
photon
promote
state
*4DPAPN•-.
Employing
ultrafast
transient
absorption
spectroscopy,
here
we
report
that,
although
indeed
involved
transformation,
*4DPAPN•-
short-lived,
not
emissive,
quenched
organic
substrate
employed
reaction,
opposite
what
authors.
can
solvated
able
reduce
chemistry.
It
worth
noting
different
photochemical
likely
be
operative
CH2Cl2,
where
electrons
much
less
stabilized
solvent
might
occur.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
63(7)
Опубликована: Дек. 27, 2023
Herein,
we
report
the
use
of
isonitriles
as
alkyl
radical
precursors
in
light-mediated
hydro-
and
deuterodeamination
reactions.
The
reaction
is
scalable,
shows
broad
functional
group
compatibility
potential
to
be
used
late-stage
functionalization.
Importantly,
method
general
for
C
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(22)
Опубликована: Март 28, 2024
Abstract
Configurationally‐defined
dienes
are
pervasive
across
the
bioactive
natural
product
spectrum,
where
they
typically
manifest
themselves
as
sorbic
acid‐based
fragments.
These
C
5
motifs
reflect
biosynthesis
algorithms
that
facilitate
their
construction.
To
complement
established
biosynthetic
paradigms,
a
chemical
platform
to
construction
of
stereochemically
defined,
functionalizable
by
light‐enabled
isomerization
has
been
devised.
Enabled
selective
energy
transfer
catalysis,
variety
substituted
β‐boryl
acid
derivatives
can
be
isomerized
in
regio‐
and
stereo‐selective
manner
(up
97
:
3).
Directionality
is
guided
stabilizing
n
O
→p
B
interaction
product:
this
constitutes
formal
anti
‐hydroboration
starting
alkyne.
This
operationally
simple
reaction
employs
low
catalyst
loadings
(1
mol
%)
complete
1
h.
X‐ray
analysis
supports
hypothesis
leads
chromophore
bifurcation:
provides
structural
foundation
for
transfer.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Окт. 4, 2024
The
challenging
synthesis
of
thermodynamic-unfavored
cis-olefins
through
catalytic
cross-coupling
reactions
requires
the
synergistic
interaction
substrate-activating
units
and
configuration-regulating
catalysts.
Successfully
hitting
these
two
birds
with
one
stone,
we
herein
develop
a
convenient
photoredox
access
to
Z-alkenes
from
alkynes
light
alkanes
bifunctional
iron-catalyzed
system
possessing
both
C(sp
