Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 17, 2025
Molecules
containing
fluoroalkyl
and
arylthio
groups
play
a
pivotal
role
in
pharmaceutical
agrochemical
development.
The
simultaneous
introduction
of
these
functional
through
the
1,2-difunctionalization
alkenes
is
an
efficient
strategy.
Fluoroalkyl
phenyl
sulfones
serve
as
accessible
radical
precursors;
however,
their
tendency
to
interact
with
thiophenol
via
electron
donor–acceptor
interaction
mechanism
can
impede
desired
transformation.
Through
meticulous
selection
solvent
base,
we
successfully
utilized
copper
catalysis
facilitate
alkene-involved
three-component
reaction.
Our
work
unveils
photoredox
copper-catalyzed
fluoroalkylation–thiolation
using
various
(such
perfluoroethyl,
tetrafluoroethyl,
trifluoromethyl,
difluoromethyl,
difluoroalkyl,
difluorobenzyl).
efficacy
this
approach
exemplified
by
synthesis
Kengreal
derivatives.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(49)
Published: Aug. 22, 2023
Abstract
Much
progress
has
been
made
in
the
development
of
methods
to
both
create
compounds
that
contain
C−F
bonds
and
functionalize
bonds.
As
such,
are
becoming
common
versatile
synthetic
functional
handles.
This
review
summarizes
advantages
defluorinative
functionalization
reactions
for
small
molecule
synthesis.
The
coverage
is
organized
by
type
carbon
framework
fluorine
attached
mono‐
polyfluorinated
motifs.
main
challenges,
opportunities
advances
discussed
each
class
organofluorine.
Most
text
focuses
on
case
studies
illustrate
how
defluorofunctionalization
can
improve
routes
targets
or
properties
enable
unique
mechanisms
reactions.
broader
goal
showcase
incorporating
exploiting
design
routes,
improvement
specific
advent
new
methods.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
62(8)
Published: Nov. 18, 2022
Several
energy-demanding
photoreactions
require
harsh
UV
light
from
inefficient
sources.
The
conversion
of
low-energy
visible
to
high-energy
singlet
states
via
triplet-triplet
annihilation
upconversion
(TTA-UC)
could
offer
a
solution
for
driving
such
reactions
under
mild
conditions.
We
present
the
first
annihilator
with
an
emission
maximum
in
UVB
region
that,
combined
organic
sensitizer,
is
suitable
blue-to-UVB
upconversion.
was
successfully
employed
as
energy
donor
subsequent
FRET
activations
aliphatic
carbonyls.
This
hitherto
unreported
UC-FRET
reaction
sequence
directly
monitored
using
laser
spectroscopy
and
applied
mechanistic
irradiation
experiments
demonstrating
feasibility
Norrish
chemistry.
Our
results
provide
clear
evidence
novel
blue
light-driven
substrate
or
solvent
activation
strategy,
which
important
context
developing
more
sustainable
light-to-chemical
systems.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(20)
Published: March 16, 2023
Monofluoroalkenes
are
nonhydrolyzable
mimetics
of
amides.
Previous
work
focused
on
the
synthesis
non-cyclic
monofluoroalkenes.
However,
diastereoselective
monofluorocyclohexenes
from
substrates
is
challenging.
Herein,
we
report
first
photocatalyzed
cascade
cyclization
reactions
readily
available
α,β-unsaturated
carbonyl
compounds
and
gem-difluoroalkenes
for
highly
functionalized
monofluorocyclohexenes.
The
reaction
shows
broad
substrate
scope
with
high
diastereoselectivity
(>30
examples,
up
to
86
%
yield,
>20
:
1
dr).
post-reaction
transformations
products
demonstrate
synthetic
potential
this
methodology.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(31), P. 5916 - 5921
Published: July 27, 2023
A
copper-catalyzed
trifluoromethylthio-arylsulfonylation
between
1,3-enynes,
AgSCF3,
aryldiazonium
tetrafluoroborates,
and
SO2
(from
SOgen)
is
presented,
which
could
introduce
sulfone,
SCF3,
allene
moieties
into
one
molecule
simultaneously.
This
strategy
features
mild
reaction
conditions,
good
substrate
compatibility,
excellent
regioselectivity.
The
products
obtained
have
the
potential
for
further
conversion
other
valuable
compounds.
Initial
investigations
mechanism
suggest
that
it
may
proceed
via
a
radical
pathway.
Notably,
SOgen
was
proven
as
uniquely
effective
surrogate
in
this
transformation.
Green Chemistry,
Journal Year:
2023,
Volume and Issue:
25(23), P. 9672 - 9679
Published: Jan. 1, 2023
A
H
2
O-promoted
and
(NH
4
)
CO
3
-enabled
defluoroiminization
reaction
of
fluoroalkyl
alkenes
for
the
synthesis
fluoroalkylated
1,5-diazapentadienes
has
been
developed.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(8), P. 1336 - 1341
Published: Feb. 23, 2023
A
concise
Fe-catalyzed
alkylazidation
of
α-trifluoromethylalkenes
via
a
C–C
bond
cleavage/radical
addition/azidation
cascade
is
described.
This
protocol
features
broad
substrate
scope,
excellent
functional
group
compatibility,
and
the
ability
to
be
performed
on
gram
scale,
thus
offering
practical
step-economic
approach
synthetically
useful
tertiary
α-trifluoromethyl
azides.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(20), P. 3745 - 3749
Published: May 11, 2023
The
auxiliary
function
of
a
carbonyl
group
in
the
tunable
defluorophosphination
and
defluorophosphorylation
trifluoromethylated
enones
with
P(O)-containing
compounds
was
demonstrated.
Controlled
replacement
one
or
two
fluorine
atoms
while
maintaining
high
chemo-
stereoselectivity
achieved
under
mild
conditions,
thus
enabling
diversity-oriented
synthesis
skeletally
diverse
organophosphorus
libraries─(Z)-difluoro-1,3-dien-1-yl
phosphinates,
(1Z,3E)-4-phosphoryl-4-fluoro-buta-1,3-dien-1-yl
(E)-4-phosphoryl-4-fluoro-1,3-but-3-en-1-ones─in
good
yields
excellent
functional
tolerance.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(18)
Published: Jan. 6, 2024
Hydroxytrifluoroethyl
and
trifluoroacetyl
groups
are
of
utmost
importance
in
biologically
active
compounds,
but
methods
to
tether
these
motifs
organic
architectures
have
been
limited.
Typically,
the
preparation
compounds
relied
on
use
strong
bases
or
multistep
routes.
The
renaissance
radical
chemistry
photocatalytic,
transition
metal
mediated,
hydrogen
atom
transfer
(HAT)
processes
allowed
installation
medicinally
relevant
fluorinated
motifs.
This
review
provides
an
overview
available
for
direct
synthesis
hydroxytrifluoroethyl-
trifluoroacetyl-derived
governed
by
single-electron
processes.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(6), P. 1282 - 1286
Published: Feb. 1, 2024
Dithioacetals
are
a
frequently
used
motif
in
synthetic
organic
chemistry,
and
most
existing
reports
discuss
only
symmetrical
dithioacetals.
Examples
of
unsymmetrical
dithioacetals
scarce,
few
general
methods
for
the
selective
synthesis
these
compounds
exists.
An
intriguing
visible-light-induced
strategy
has
been
established
this
work
sequential
reactions
S–H
insertion
acetal
exchange
between
acylsilanes
two
different
thiols
that
deliver
wide
variety
moderate
yields.
The
were
obtained
with
high
selectivity,
great
functional
groups
tolerated.