Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(20), P. 4351 - 4355
Published: May 10, 2024
We
report
a
novel
three-component
radical
acylfluoroalkylation
of
1,3-enynes
by
synergistic
N-heterocyclic
carbene
(NHC)/photoredox
catalysis
toward
various
fluorinated
allenic
aryl
ketones.
This
protocol
features
broad
substrate
scope
and
excellent
functional
group
tolerability,
with
examples
late-stage
modification
drug
molecules
natural
products.
Notably,
seven
different
fluoroalkyl
motifs
can
be
introduced
to
1,3-enynes,
further
demonstrating
the
robustness
generality
this
method.
The
generation
from
each
sulfinate
reagent
was
individually
supported
EPR
experiments.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(7), P. 2112 - 2133
Published: Jan. 1, 2024
Organofluorine
compounds
are
of
high
value.
NHC-catalyzed
fluorination
and
fluoroalkylation
have
served
as
powerful
versatile
vehicles
for
accessing
the
related
organofluorines.
This
review
focuses
on
recent
developments
in
this
area.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(18), P. 12386 - 12394
Published: March 19, 2024
Difluoromethylation
reactions
are
increasingly
important
for
the
creation
of
fluorine-containing
heterocycles,
which
core
groups
in
a
diverse
range
biologically
and
pharmacologically
active
ingredients.
Ideally,
this
typically
challenging
reaction
could
be
performed
photocatalytically
under
mild
conditions.
To
achieve
separation
redox
processes
would
required
efficient
generation
difluoromethyl
radicals
reduction
oxygen.
A
covalent
organic
framework
photocatalytic
material
was,
therefore,
designed
with
dual
reactive
centers.
Here,
anthracene
was
used
as
site
benzothiadiazole
an
oxidation
site,
distributed
tristyryl
triazine
framework.
Efficient
charge
ensured
by
superior
electron-donating
-accepting
abilities
centers,
creating
long-lived
photogenerated
electron–hole
pairs.
Photocatalytic
difluoromethylation
16
compounds
high
yields
remarkable
functional
group
tolerance
demonstrated;
included
bioactive
molecules
such
xanthine
uracil.
The
structure–function
relationship
dual-active-center
photocatalyst
investigated
through
electron
spin
resonance,
femtosecond
transient
absorption
spectroscopy,
density
theory
calculations.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(44)
Published: Sept. 16, 2022
Fluorinated
fused
rings
are
challenging
to
construct
from
simple
starting
materials.
Herein,
we
report
the
first
photocatalyzed
cascade
reactions
of
readily
available
cyclopropanols
and
α-trifluoromethyl-substituted
olefins
for
synthesis
gem-difluorooxetanes.
Two
three
bonds
were
efficiently
constructed
in
one
reaction.
The
reaction
showed
broad
substrate
scope
downstream
transformations
products
demonstrated
synthetic
potential
mechanistic
study
supported
presence
photoredox
catalysis
energy
transfer
catalysis/direct
photo-excitation
processes.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(12), P. 7756 - 7794
Published: May 25, 2023
A
selection
of
perfluoroalkylation
reactions
aliphatic
substrates
that
display
methodological
and
synthetic
amplitude
will
be
studied,
giving
examples
their
applications
mechanistic
details.
An
array
approaches
for
fluoroalkylation
are
documented;
in
particular,
radical
protocols
prominent
among
methods.
To
effect,
addition
perfluoroalkyl
radicals
RF
(RF=CnF2n+1,
n
>
1)
to
unsaturated
organic
serve
as
one
the
most
direct
efficacious
ways
access
fluoroalkylated
scaffolds.
The
syntheses
perfluoroalkyl-substituted
vinyl,
alkynyl,
allylic
compounds;
hydro-,
iodo-,
oxy-perfluoroalkylated
alkanes
olefins;
carbonyl
enamides,
amides,
thioamides,
hydrazones;
multicomponent
studied.
While
there
a
number
accomplished
reports
on
organofluorination,
we
aim
provide
an
overview
radical-involved
substrates,
covering
from
2018
early
2023,
summarized
Tables
1–4.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(15), P. 3898 - 3902
Published: Jan. 1, 2023
An
efficient
electrochemical
synthesis
of
fluoroethylated
benzoxazines
via
oxyfluoromethylation
was
developed.
The
broad
applicability
and
general
utility
were
tested
highlighted
by
the
substrate
scope
late-stage
synthesis.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(2), P. 1276 - 1281
Published: Jan. 5, 2024
The
first
efficient
access
to
N-difluoromethyl
amides,
carbamates,
thiocarbamates,
ureas,
formamides,
and
their
derivatives
is
reported
herein.
synthetic
strategy
relies
on
the
initial
synthesis
straightforward
derivatization
of
N-CF2H
carbamoyl
fluorides,
which
were
prepared
through
a
desulfurization–fluorination
thioformamides
(─NH─C(H)═S)
coupled
with
carbonylation.
newly
made
carbonyl
compounds
proved
be
highly
robust
compatible
numerous
chemical
transformations
downstream
derivatizations,
underscoring
potential
this
novel
motif
as
building
block
in
complex
functional
molecules.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(14), P. 4024 - 4040
Published: Jan. 1, 2024
This
review
provides
a
comprehensive
overview
of
metal
catalysis
in
photo-electrochemical
systems,
discussing
reaction
mechanisms
and
offering
prospects
for
this
triadic
catalytic
mode.
Chinese Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
43(12), P. 4213 - 4213
Published: Jan. 1, 2023
Benzoxazines
are
important
motif
in
pharmaceuticals
and
functional
molecules.A
visible-light
induced
photocatalytic
strategy
for
the
synthesis
of
difluoroethyl
benzoxazines
with
organo-photocatalyst
was
developed.In
present
protocol,
a
series
olefinic
amides
can
be
transferred
to
difluoroethylated
via
oxydifluoromethylation
CF2HSO2Na
as
difluoromethylating
reagent,
which
is
easily
operated
good
group
tolerant.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(12)
Published: Jan. 24, 2023
A
simple
process
for
the
oxy-monofluoromethylation
of
alkenes
is
described.
In
combination
with
visible-light
copper(I)
photoredox
catalysis,
an
easily
accessible
iodine(III)
reagent
containing
monofluoroacetoxy
ligands
serves
as
a
powerful
source
monofluoromethyl
(CH2
F)
radical,
enabling
step
economical
synthesis
γ-fluoro-acetates
from
broad
range
olefinic
substrates
under
mild
conditions.
Applications
to
late-stage
diversification
derived
complex
molecules,
amino
acids
and
fluoromethylated
heterocycles
are
also
demonstrated.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(5), P. 3509 - 3524
Published: Feb. 16, 2024
A
photocatalytic
annulation
cascade
of
unactivated
N-alkene-linked
indoles
with
Langlois'
reagent
by
a
radical
relay
is
developed
at
room
temperature
under
blue
LED
irradiation.
The
reaction
afforded
series
tri/difluoromethylated
pyrrolo[1,2-a]indoles
in
moderate
to
good
yields.
DFT
study
suggests
that
the
ascribed
rhodamine
6G-induced
cyclization
involving
vinyl
addition-radical
and
hydrogen-atom-abstraction
(HAA)
processes,
interestingly,
are
applied
as
fluorescent
dyes
into
fluorescence
spectrum
live-cell
imaging.
This
paper
represents
an
initial
example
on
cascades
HAA
process.
