Organic Letters,
Journal Year:
2019,
Volume and Issue:
21(10), P. 3769 - 3773
Published: May 7, 2019
A
visible-light-promoted
redox
neutral
γ,γ-difluoroallylation
of
cycloketone
oxime
ethers
with
trifluoromethyl
alkenes
through
C–C
and
C–F
bond
cleavage
has
been
achieved,
which
affords
various
cyano-substituted
gem-difluoroalkenes
in
generally
good
yields.
The
reaction
provides
a
facile
protocol
for
forming
gem-difluoroalkene
functionality
cyano
group
while
incorporating
them
into
one
molecule.
conversion
the
resulting
to
cyclic
monofluoroalkenes
via
second
was
also
described.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(2), P. 2695 - 2751
Published: Oct. 21, 2021
Radical
aryl
migrations
are
powerful
techniques
to
forge
new
bonds
in
aromatic
compounds.
The
growing
popularity
of
photoredox
catalysis
has
led
an
influx
novel
strategies
initiate
and
control
migration
starting
from
widely
available
radical
precursors.
This
review
encapsulates
progress
enabled
by
photochemical
methods─particularly
catalysis─since
2015.
Special
attention
is
paid
descriptions
scope,
mechanism,
synthetic
applications
each
method.
Organic Letters,
Journal Year:
2019,
Volume and Issue:
21(8), P. 2658 - 2662
Published: April 3, 2019
A
photoinduced,
phosphoranyl
radical-mediated
protocol
for
the
direct
N–O
cleavage
of
strained
cycloketone
oximes
via
a
polar/SET
crossover
process
was
developed
first
time.
This
visible-light-driven
activation
mode
oxime
offers
beneficial
features
such
as
streamlined
synthetic
and
versatile
photochemical
reactivities.
Consequently,
alkenes
α-trifluoromethyl
with
varied
electronic
structural
acted
competent
radical
receptors
in
this
protocol,
enabling
facile
accesses
to
range
elongated
cyano
and/or
gem-difluoroalkene-bearing
compounds.
Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: June 29, 2021
Abstract
Hydrogen
atom
abstraction
(HAT)
from
C(
sp
3
)–H
bonds
of
naturally
abundant
alkanes
for
alkyl
radical
generation
represents
a
promising
yet
underexplored
strategy
in
the
alkylation
reaction
designs
since
involving
stoichiometric
oxidants,
excessive
alkane
loading,
and
limited
scope
are
common
drawbacks.
Here
we
report
photo-induced
chemical
oxidant-free
cross-dehydrogenative
coupling
(CDC)
between
heteroarenes
using
catalytic
chloride
cobalt
catalyst.
Couplings
strong
bond-containing
substrates
complex
heteroarenes,
have
been
achieved
with
satisfactory
yields.
This
dual
platform
features
situ
engendered
chlorine
exploits
cobaloxime
catalyst
to
enable
hydrogen
evolution
turnover.
The
practical
value
this
protocol
was
demonstrated
by
gram-scale
synthesis
alkylated
heteroarene
merely
equiv.
loading.
Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: March 22, 2021
Abstract
The
intermolecular
three-component
alkene
vicinal
dicarbofunctionalization
(DCF)
reaction
allows
installation
of
two
different
carbon
fragments.
Despite
extensive
investigation
into
its
ionic
chemistry,
the
enantioseletive
radical-mediated
versions
DCF
reactions
remain
largely
unexplored.
Herein,
we
report
an
intermolecular,
enantioselective
radical
olefins
enabled
by
merger
addition
and
cross-coupling
using
photoredox
copper
dual
catalysis.
Key
to
success
this
protocol
relies
on
chemoselective
acyl
cyanoalkyl
radicals,
generated
in
situ
from
redox-active
oxime
esters
a
photocatalytic
N-centered
iminyl
radical-triggered
C-C
bond
cleavage
event,
onto
alkenes
form
new
radicals.
Single
electron
metalation
such
newly
formed
radicals
TMSCN-derived
L1
Cu(II)(CN)
2
complex
leads
asymmetric
cross-coupling.
This
process
proceeds
under
mild
conditions,
tolerates
diverse
range
functionalities
synthetic
handles,
leading
valuable
optically
active
β
–cyano
ketones
alkyldinitriles,
respectively,
highly
manner
(>60
examples,
up
97%
ee).
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
25(5), P. 1975 - 1981
Published: Jan. 1, 2023
This
study
describes
a
green
and
sustainable
photoinduced
strategy
for
decarboxylative
C–H
(amino)alkylation
of
heteroarenes
with
carboxylic
acids
under
metal-
photosensitizer-free
conditions.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(23), P. 8993 - 8999
Published: Jan. 1, 2024
The
aromatization-driven
deconstructive
coupling
of
spiro
carbocycles
with
organic
halides
via
dual
photoredox/nickel
catalysis
is
developed.
An
in-depth
mechanism
study
revealed
that
this
reaction
proceeded
a
radical-metal
crossover
pathway.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(18), P. 5122 - 5129
Published: Jan. 1, 2024
This
study
demonstrates
a
strategy
involving
photoinduced
energy
transfer
for
decarboxylative
Minisci
C–H
(amino)alkylation
of
heteroarenes
employing
diverse
oxime
esters
(from
carboxylic
acids)
as
(amino)alkylating
reagents.
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
58(8), P. 2402 - 2406
Published: Dec. 19, 2018
The
palladium-catalyzed
Heck
reaction
is
a
well-known,
Nobel
Prize
winning
transformation
for
producing
alkenes.
Unlike
the
alkenyl
and
aryl
variants
of
reaction,
alkyl-Heck
still
underdeveloped
owing
to
competitive
side
reactions
alkyl-palladium
species.
Herein,
we
describe
development
deaminative
alkyl-Heck-type
that
proceeds
through
C-N
bond
activation
by
visible-light
photoredox
catalysis.
A
variety
aliphatic
primary
amines
were
found
be
efficient
starting
materials
this
new
process,
affording
corresponding
alkene
products
in
good
yields
under
mild
conditions.
Moreover,
strategy
was
successfully
applied
carbonylative
reactions.
Chemical Science,
Journal Year:
2018,
Volume and Issue:
9(27), P. 5883 - 5889
Published: Jan. 1, 2018
Fine-tuned
organic
photoredox
catalysts
are
introduced
for
the
metal-free
alkynylation
of
alkylnitrile
radicals
generated
via
oxidative
ring
opening
cyclic
alkylketone
oxime
ethers.
Angewandte Chemie International Edition,
Journal Year:
2017,
Volume and Issue:
57(6), P. 1692 - 1696
Published: Dec. 20, 2017
Abstract
A
method
for
site‐specific
intermolecular
γ‐C(sp
3
)−H
functionalization
of
ketones
has
been
developed
using
an
α‐aminoxy
acid
auxiliary
applying
photoredox
catalysis.
Regioselective
activation
inert
C−H
bond
is
achieved
by
1,5‐hydrogen
atom
abstraction
oxidatively
generated
iminyl
radical.
Tertiary
and
secondary
C‐radicals
thus
formed
at
the
γ‐position
imine
functionality
undergo
radical
conjugate
addition
to
various
Michael
acceptors
provide,
after
reduction
hydrolysis,
corresponding
γ‐functionalized
ketones.
