The
present
chapter
aims
at
introducing
the
main
approaches
to
developing
photocatalytic
synthetic
methods
by
using
water
as
a
reaction
medium.
By
merging
innate
green
properties
of
with
exploitation
renewable
energy
source,
such
light,
this
field
research
represents
one
most
intensive
ones.
A
selection
literature
available
so
far
is
divided
into
three
sections
based
on
(i)
solubility
photocatalyst
and
use
additives
including
surfactants
(photomicellar
catalysis);
(ii)
on-water
conditions
achieve
acceleration
rates;
(iii)
photobiocatalytic
methods.
latter,
indeed,
are
intrinsically
designed
optimized
be
performed
in
an
aqueous
environment.
Taken
together,
all
reactions
herein
highlighted
offer
unique
opportunities
address
challenge
sustainable
manufacturing
chemicals.
Molecules,
Journal Year:
2024,
Volume and Issue:
29(3), P. 569 - 569
Published: Jan. 23, 2024
Radical
reactions
in
water
or
aqueous
media
are
important
for
organic
synthesis,
realizing
high-yielding
processes
under
non-toxic
and
environmentally
friendly
conditions.
This
overview
includes
(i)
a
general
introduction
to
chemistry
media,
(ii)
synthetic
approaches
in,
on,
with
as
well
heterogeneous
phases,
(iii)
of
carbon-centered
radicals
(or
deuterium
oxide)
activated
through
coordination
various
Lewis
acids,
(iv)
photocatalysis
(v)
applications
bioinspired
by
naturally
occurring
processes.
A
wide
range
chemical
strategies
different
experimental
conditions
have
been
reviewed
that
lead
functional
group
translocation
transformation
reactions,
leading
the
preparation
complex
molecules.
These
results
reveal
how
solvent/medium/reagent
radical
has
matured
over
last
two
decades,
further
discoveries
anticipated
near
future.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(24), P. 6124 - 6130
Published: Jan. 1, 2023
We
herein
describe
a
three-component
radical
acylmonofluoromethylation
of
alkenes
by
cooperative
NHC/photoredox
catalysis
to
synthesize
various
monofluorinated
alkyl
aryl
ketones.
New Journal of Chemistry,
Journal Year:
2023,
Volume and Issue:
47(44), P. 20642 - 20652
Published: Jan. 1, 2023
We
report
a
photo-redox
catalyzed
radical
C–H
monofluoromethylation
of
heterocycles,
thus
demonstrating
this
process
and
the
importance
monofluoromethyl
unit
in
medicinal
drug
discovery
purposes.
Synthesis,
Journal Year:
2024,
Volume and Issue:
56(09), P. 1415 - 1421
Published: Jan. 17, 2024
Abstract
An
environmentally
friendly
iodine-promoted
disproportionate
coupling
reaction
of
arylsulfonyl
hydrazides
is
reported.
This
strategy
can
synthesize
thiosulfonates
with
medium
to
excellent
yields,
and
features
a
green
system,
wide
applicability
substrates,
easy
availability
raw
materials.
The
preliminary
mechanistic
study
reveals
that
iodine
plays
an
important
role
in
the
radical
process.
European Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
27(24)
Published: April 24, 2024
Abstract
We
report
an
unprecedented
Ni‐catalyzed
direct
monofluoromethylthiolation
of
acyl
chlorides,
in
situ
generated
from
carboxylic
acids,
with
elemental
sulfur
(S
8
)
as
the
S
source
and
fluoroiodomethane
(ICH
2
F)
CH
F
radical
to
produce
a
series
monofluoromethylthioesters
moderate
good
yields.
This
approach
features
excellent
functional
group
tolerance
broad
substrate
scope.
Additionally,
late‐stage
complex
bioactive
molecules
can
also
be
accomplished
using
this
method.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(16), P. 11747 - 11752
Published: July 31, 2024
The
radical
1,3-hydro-di/monofluoromethylation
of
N,N'-cyclic
azomethine
imines
with
HCF2SO2Na/H2CFSO2Na
via
photoredox
catalysis
is
described.
This
reaction
exhibits
broad
functional
group
compatibility,
providing
the
desired
products
in
good
yields.
However,
CF3SO2Na
failed
to
produce
trifluoromethyl
product.
DFT
calculations
revealed
that
transition
state
activation
energy
for
trifluoromethylation
was
significantly
higher
and
isotropic
charge
repulsion
makes
it
difficult
CF3
transfer
electrons.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(30), P. 6449 - 6453
Published: July 22, 2024
Herein,
we
report
a
visible-light-induced
iridium-promoted
direct
bifunctionalization
of
3-butenoic
acid
with
bromodifluoromethyl
heteroarylsulfones.
This
methodology
enables
the
concurrent
introduction
difluoromethyl
heteroarylsulfone
and
bromine
groups
into
under
mild
reaction
conditions.
Various
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(36), P. 7707 - 7712
Published: Aug. 28, 2024
Herein,
we
have
developed
a
complementary
entry
to
enable
hydroheteroarylation
of
alkenes
involving
basically
photoredox
dearomatizative
heterocyclic
carbon
radical
formation
through
acid-coupled
electron
transfer
followed
by
Giese
addition.
While
protonic
solvent
and
thiophenol
additive
enabled
two
molecular
hydroheteroarylations
alkenes,
the
nonproton
environment
with
BF