Abstract
Visible
light‐mediated
photocatalytic
approach
for
the
radical
functionalization
of
alkenes
bearing
fluorinated
aryl
sulfide
fragment
is
described.
The
process
occurs
in
presence
organic
photocatalyst
using
sulfinates
as
sources
radicals.
key
step
reaction
intramolecular
1,4‐migration
polyfluoroaryl
group.
In
reaction,
three
new
bonds
are
formed
(two
C−C
and
one
C−S
bond).
decisive
role
fluorine
atoms
efficiency
was
confirmed
by
DFT
calculations.
Chinese Journal of Chemistry,
Год журнала:
2021,
Номер
40(5), С. 582 - 588
Опубликована: Ноя. 10, 2021
Comprehensive
Summary
A
radical‐induced
1,2‐
α
‐boryl
migration
through
radical
polar
crossover
reactions
has
been
described.
In
this
work,
in
situ
formed
vinyldiboron
“ate”
complexes
from
alkenyl
Grignard
reagent
and
diborylalkanes
react
with
commercial
precursors
under
light
initiation.
This
three‐component
process
enables
diborylation
of
alkene.
protocol
features
high
atom
economy,
a
broad
substrate
scope
as
well
good
functional
group
toleration
mild
conditions.
The Chemical Record,
Год журнала:
2022,
Номер
23(9)
Опубликована: Ноя. 11, 2022
Abstract
Fluorine
incorporation
by
concomitant
fluoroalkyl
radical
addition
to
alkene
or
alkyne
and
functional
group
migration
(FGM)
represents
an
ingenious
robust
strategy
for
the
synthesis
of
structurally
diverse
fluorinated
compounds.
This
account
gives
overview
related
studies
in
our
group,
which
three
main
reaction
modes
are
discussed:
1)
fluoroalkylative
difunctionalization
unactivated
alkenes
via
intramolecular
FGM;
2)
docking‐migration
process
using
fluoroalkyl‐containing
bifunctional
reagents;
3)
into
C(sp
3
)−H
bond
consecutive
hydrogen
atom
transfer
(HAT)
FGM.
Relying
on
these
methods,
a
variety
trifluoromethylation
di‐/mono‐fluoroalkylation
reactions
along
with
cyano,
heteroaryl,
oximino,
formyl,
alkynyl,
alkenyl
groups
have
been
accomplished
under
mild
conditions.
A
novel
Ru-catalyzed
radical-triggered
trifunctionalization
of
hexenenitriles
is
presented,
employing
a
strategy
remote
cyano
group
migration
and
meta-C(sp2)-H
functionalization.
Through
migration,
the
alkenyl
moiety
undergoes
difunctionalization
to
formation
benzylic
radical
intermediate.
This
intermediate
facilitates
para-selective
C-H
bond
addition
relative
C-Ru
within
Ru(III)
complex,
ultimately
enabling
trifunctionalization.
methodology
provides
an
efficient
route
diverse
array
nitrile-containing
compounds
with
broad
functional
compatibility.
In
comparison
to
alkyl
monoboron
or
1,2-diboron,
which
can
generate
radicals
via
tetracoordinate
boron
species
under
photocatalytic
conditions,
the
participation
of
gem-diborons
as
substrates
in
such
reactions
remains
be
developed.
Herein,
we
report
a
method
utilizing
starting
materials
α-boryl
radicals,
then
react
with
various
olefins,
successfully
and
efficiently
constructing
diverse
range
high-value
homoallylic
boronates;
meanwhile,
gem-difluorohomoallylic
skeletons
could
also
smoothly
obtained.
This
transformation
demonstrates
broad
substrate
scope
excellent
tolerance
toward
functional
groups,
enhancing
utility
gem-diboron
precursors
for
C-C
bond
construction
production
valuable
products.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(29)
Опубликована: Апрель 30, 2024
An
electrochemical
radical
Truce
Smiles
rearrangement
of
N-allylbenzamides
is
documented
herein.
The
selective
1,4-aryl
migration
was
triggered
by
the
fluoromethylation
alkene
providing
a
direct
route
to
fluoro
derivatives
highly
privileged
β-arylethylamine
pharmacophore.
This
practical
transformation
utilizes
readily
available
starting
materials
and
employs
an
electrical
current
drive
oxidative
process
under
mild
reaction
conditions.
It
accommodates
variety
migratory
aryl
groups
with
different
electronic
properties
substitution
patterns.
Careful
selection
protecting
group
on
nitrogen
atom
N-allylbenzamide
crucial
outcompete
undesired
6-endo
cyclization
achieve
high
level
selectivity
towards
migration.
DFT
calculations
support
mechanism
unveil
origin
between
two
competitive
pathways.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Авг. 30, 2024
Herein,
a
palladium-catalyzed
1,3-alkynyl
migration
of
allylic
alcohol
for
the
synthesis
β-alkynyl
ketone
was
described.
This
intramolecular
rearrangement
reaction
demonstrated
an
enhanced
reactivity
compared
to
traditional
intermolecular
alkynylation
by
circumventing
dimerization
alkynes,
exhibiting
specific
selectivity
toward
elimination.
Moreover,
this
featured
wide
substrate
scope,
good
functional
group
tolerance,
and
100%
atom
economy.
Organic Letters,
Год журнала:
2023,
Номер
25(22), С. 4168 - 4172
Опубликована: Май 26, 2023
Described
here
is
a
simple
and
efficient
method
to
prepare
organoboron
compounds
through
α-deprotonation
functionalization
of
benzylboronates.
In
addition
alkyl
halides,
chlorosilane,
deuterium
oxide,
trifluoromethyl
alkene
could
also
serve
as
electrophiles
in
this
approach.
Notably,
the
boryl
group
enables
high
diastereoselectivities
when
unsymmetrical
secondary
α-bromoesters
are
used.
This
methodology
exhibits
broad
substrate
scope
atomic
efficiency
offers
an
alternative
C-C
bond
disconnection
for
synthesis
Chemical Science,
Год журнала:
2023,
Номер
14(43), С. 12083 - 12090
Опубликована: Янв. 1, 2023
Nitrogen
containing
compounds,
such
as
anilines,
are
some
of
the
most
widespread
and
useful
chemical
species,
although
their
high
unselective
reactivity
has
prevented
incorporation
into
many
interesting
transformations,
functionalization
alkenes.
Herein
we
report
a
method
that
allows
trifluoromethylarylation
alkenes
using
for
first
time,
with
no
need
additives,
transition
metals,
photocatalysts
or
an
excess
reagents.
An
in-depth
mechanistic
study
reveals
key
role
hexafluoroisopropanol
(HFIP)
unique
solvent,
establishing
hydrogen
bonding
network
aniline
trifluoromethyl
reagent,
is
responsible
altered
exquisite
selectivity.
This
work
uncovers
new
mode
involves
use
abundant
anilines
non-prefunctionalized
aromatic
source
simultaneous
activation
hypervalent
iodine
reagent.
Organic Chemistry Frontiers,
Год журнала:
2023,
Номер
10(9), С. 2332 - 2339
Опубликована: Янв. 1, 2023
We
describe
a
catalyst-free
visible-light
mediated
akynylperfluoroalkylation
of
unactive
alkenes
with
perfluoroalkyl
iodides,
which
provides
series
α-perfluoroalkyl-β-alkynyl
ketone
derivatives.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(41)
Опубликована: Июль 18, 2024
Abstract
Although
highly
appealing
for
rapid
access
of
molecular
complexity,
multi‐functionalization
alkenes
that
allows
incorporation
more
than
two
functional
groups
remains
a
prominent
challenge.
Herein,
we
report
novel
strategy
merges
dipolar
cycloaddition
with
photoredox
promoted
radical
ring‐opening
remote
C(sp
3
)−H
functionalization,
thus
enabling
smooth
1,2,5‐trifunctionalization
unactivated
alkenes.
A
regioselective
[3+2]
anchors
reaction
trigger
onto
alkene
substrates.
The
subsequent
halogen
atom
transfer
(XAT)
selectively
initiates
process,
which
is
followed
by
series
1,5‐hydrogen
(1,5‐HAT)
and
intermolecular
fluorine
(FAT)
events.
With
this
method,
site‐selective
introduction
three
different
accomplished
broad
spectrum
valuable
β‐hydroxyl‐ϵ‐fluoro‐nitrile
products
are
synthesized
from
readily
available
terminal
