Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(7), P. 1545 - 1550
Published: Feb. 8, 2024
Abstract
Manganese
(Mn)
is
the
third
most
abundant
transition
metal
on
Earth
and
known
for
its
exceptional
biocompatibility.
The
development
of
novel
catalytic
mode
Mn
great
significance
to
advancing
organic
synthesis.
In
this
study,
first
manganese
(Mn)‐catalyzed
[2+2+2]
cycloaddition
alkynes
achieved
with
aid
visible‐light
photoredox
catalysis.
Photoredox
catalysis
proposed
promote
transformation
by
in
situ
reduction
high‐valent
Mn(II)
complex
Mn(0)
species,
thereby
initiating
reaction.
Additionally,
a
photooxidation‐induced
reductive
ellimination
step
also
suggested.
This
system
further
distinguished
notable
tolerance
towards
both
terminal
internal
as
counterparts
diynes.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(3), P. 1300 - 1310
Published: Jan. 11, 2024
Directly
utilizing
abundant
and
inexpensive
sources
of
aliphatic
carboxylic
acids
is
highly
attractive
for
the
synthesis
CF2H-
CH3-containing
compounds.
Herein,
we
report
a
versatile
photoinduced
iron-catalyzed
platform
hydrodifluoromethylation
hydromethylation
alkenes
without
need
additional
stoichiometric
oxidants.
These
two
transformations
are
accomplished
by
visible-light-induced
ligand-to-iron
charge
transfer
open-shell
activation
system
using
industrial
chemical
difluoroacetic
acetic
as
precursors
postulated
to
operate
via
difluoromethyl
methyl
radical-mediated
decarboxylation
mechanism.
Experimental
results
show
that
strategy
also
applicable
difunctionalization
unactivated
alkenes.
Meanwhile,
this
provides
viable
route
pharmaceutically
active
molecules
containing
deuterated
units.
The
protocol
exhibits
several
features,
including
mild
reaction
conditions,
divergent
radical
precursors,
operational
simplicity
scalability,
good
chemo-
regioselectivity,
scalability
supported
continuous
flow
technology,
ability
provide
high-value
building
blocks
applications
in
one
step.
JACS Au,
Journal Year:
2025,
Volume and Issue:
5(2), P. 684 - 692
Published: Feb. 2, 2025
Herein,
we
report
a
scalable
and
mild
strategy
for
the
monofluoroalkylation
of
wide
array
Giese
acceptors
via
visible-light-mediated
photoredox
catalysis
in
continuous
flow.
The
use
flow
technology
significantly
enhances
productivity
scalability,
whereas
mildness
conditions
functional
group
tolerance
are
ensured
by
leveraging
4CzIPN,
transition-metal-free
organic
photocatalyst.
Structurally
diverse
secondary
tertiary
monofluoroalkyl
radicals
can
thus
be
accessed
from
readily
available
α-monofluorocarboxylic
acids.
Given
reaction
conditions,
this
protocol
is
also
amenable
to
late-stage
functionalization
biologically
relevant
molecules
such
as
menthol,
amantadine,
bepotastine,
estrone
derivatives,
rendering
it
suitable
application
drug
discovery
programs,
which
introduction
fluorinated
fragments
highly
sought
after.
This
method
was
extended
enable
reductive
multicomponent
radical-polar
crossover
transformation
rapidly
increase
complexity
assembled
architectures
single
synthetic
operation.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: Dec. 23, 2022
Given
the
widespread
significance
of
vicinal
diamine
units
in
organic
synthesis,
pharmaceuticals
and
functional
materials,
as
well
privileged
molecular
catalysts,
an
efficient
practical
strategy
that
avoids
use
stoichiometric
strong
oxidants
is
highly
desirable.
We
herein
report
application
ligand-to-metal
charge
transfer
(LMCT)
excitation
to
1,2-diazidation
reactions
from
alkenes
TMSN
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
52(17), P. 6120 - 6138
Published: Jan. 1, 2023
In
recent
years,
the
activation
of
unactivated
alkyl
chlorides
through
light-induced
processes
has
emerged
as
a
promising
field
in
radical
chemistry,
and
led
to
new
transformations
organic
synthesis.
Direct
utilization
C(sp3)-hybridized
electrophiles
enables
facile
construction
carbon-carbon
carbon-heteroatom
bonds.
Furthermore,
studies
medicinal
chemistry
indicate
that
their
presence
is
associated
with
high
levels
success
clinical
trials.
This
review
summarizes
advances
photoinduced
discusses
mechanistic
aspects
underlying
these
reactions.
We
anticipate
this
will
serve
valuable
resource
for
researchers
chemical
bond
functionalization,
inspire
considerable
developments
drug
synthesis,
materials
science
other
related
disciplines.
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
25(8), P. 3095 - 3102
Published: Jan. 1, 2023
A
regiodivergent
electrochemical
defluorocarboxylation
of
gem
-difluorocyclopropanes
is
realized,
providing
access
to
branched
and
linear
carboxylated
monofluorinated
alkenes.
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
25(10), P. 4122 - 4128
Published: Jan. 1, 2023
A
visible
light-initiated
manganese-catalyzed
radical
hydrosulfonylation
of
a
wide
range
structurally
diverse
alkenes
using
commercially
available
and
relatively
cheap
sulfonyl
chlorides
as
sources
is
described.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(29), P. 6197 - 6202
Published: July 15, 2024
A
silver-promoted
three-component
heterocyclization
of
alkynes,
perfluoroalkyl
halides,
and
1,3-dinucleophiles
was
developed
for
the
efficient
synthesis
privileged
(E)-perfluoroalkenyl
pyrroles.
The
reaction
proceeded
through
a
rationally
designed
sequence
radical
perfluoroalkylation
intramolecular
defluorinative
[3
+
2]-heterocyclization.
utility
halide
as
perfluoroalkenyl
reagent,
by
selective
controllable
functionalization
two
inert
C(sp3)–F
bonds
at
vicinal
carbon
centers
on
chain,
provides
new
mode
value-added
organofluorides
starting
from
easily
available
low-cost
fluorinated
feedstock.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(41), P. 7677 - 7684
Published: Oct. 10, 2022
A
general
and
mild
strategy
involving
three-component
carboarylation
of
unactivated
alkenes
with
protic
C(sp3)–H
feedstocks
via
photoredox
catalysis
was
reported.
This
catalytic
system
is
compatible
a
broad
range
alkenes,
cyano-substituted
arenes,
diverse
feedstocks.
The
synthetic
value
this
protocol
demonstrated
by
the
late-stage
functionalization
complex
molecules
synthesis
antiallergies
including
pheniramine,
chlorpheniramine,
brompheniramine.
