Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(38)
Published: June 24, 2022
Recently
the
fruitful
merger
of
organoboron
chemistry
and
photocatalysis
has
come
to
forefront
organic
synthesis,
resulting
in
development
new
technologies
access
complex
(non)borylated
frameworks.
Central
success
this
combination
is
control
boron
hybridisation.
Contingent
on
photoactivation
mode,
as
its
neutral
planar
form
or
tetrahedral
boronate
can
be
used
regulate
reactivity.
This
Minireview
highlights
current
state
art
photocatalytic
processes
utilising
compounds,
paying
particular
attention
role
hybridisation
for
target
transformation.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
144(1), P. 137 - 144
Published: Dec. 30, 2021
A
light-driven
method
for
the
contra-thermodynamic
positional
isomerization
of
olefins
is
described.
In
this
work,
stepwise
PCET
activation
a
more
substituted
and
thermodynamically
stable
olefin
substrate
mediated
by
an
excited-state
oxidant
Brønsted
base
to
afford
allylic
radical
that
captured
Cr(II)
cocatalyst
furnish
allylchromium(III)
intermediate.
situ
protodemetalation
allylchromium
complex
methanol
highly
regioselective
affords
isomerized
less
alkene
product.
The
higher
oxidation
potential
isomer
renders
it
inert
further
oxidant,
enabling
accumulate
in
solution
over
course
reaction.
broad
range
isopropylidene
substrates
are
accommodated,
including
enol
ethers,
enamides,
styrenes,
1,3-dienes,
tetrasubstituted
alkyl
olefins.
Mechanistic
investigations
step
also
presented.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
144(1), P. 145 - 152
Published: Dec. 30, 2021
The
positional
isomerization
of
C═C
double
bonds
is
a
powerful
strategy
for
the
interconversion
alkene
regioisomers.
However,
existing
methods
provide
access
to
thermodynamically
more
stable
isomers
from
less
starting
materials.
Here,
we
report
discovery
dual
catalyst
system
that
promotes
contra-thermodynamic
under
photochemical
irradiation,
providing
terminal
directly
conjugated,
internal
utility
method
demonstrated
in
deconjugation
diverse
electron-rich/electron-poor
alkenes
and
through
strategic
application
natural
product
synthesis.
Mechanistic
studies
are
consistent
with
regiospecific
bimolecular
homolytic
substitution
(SH2′)
mechanism
proceeding
an
allyl-cobaloxime
intermediate.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(38)
Published: June 24, 2022
Recently
the
fruitful
merger
of
organoboron
chemistry
and
photocatalysis
has
come
to
forefront
organic
synthesis,
resulting
in
development
new
technologies
access
complex
(non)borylated
frameworks.
Central
success
this
combination
is
control
boron
hybridisation.
Contingent
on
photoactivation
mode,
as
its
neutral
planar
form
or
tetrahedral
boronate
can
be
used
regulate
reactivity.
This
Minireview
highlights
current
state
art
photocatalytic
processes
utilising
compounds,
paying
particular
attention
role
hybridisation
for
target
transformation.
