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.
Chemical Society Reviews,
Год журнала:
2021,
Номер
50(20), С. 11577 - 11613
Опубликована: Янв. 1, 2021
This
Review
summarizes
the
past
to
present
achievements
in
radical-mediated
rearrangements,
and
brings
up
prospects
that
may
inspire
colleagues
develop
more
useful
synthetic
tools
based
on
radical
rearrangements.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(25)
Опубликована: Апрель 11, 2024
Abstract
While
polyborylated
alkenes
are
being
recognized
for
their
elevated
status
as
highly
valuable
reagents
in
modern
organic
synthesis,
allowing
efficient
access
to
a
diverse
array
of
transformations,
including
the
formation
C−C
and
C‐heteroatom
bonds,
potential
energy‐transfer
reactive
groups
has
remained
unexplored.
Yet,
this
holds
key
generating
elusive
biradical
species,
which
can
be
captured
by
olefins,
thereby
leading
construction
new
highly‐borylated
scaffolds.
Herein,
we
report
designed
strategy
photosensitized
[2+2]‐cycloadditions
poly‐borylated
with
various
olefins
enabling
regioselective
synthesis
cyclobutane
motifs,
1,1‐di‐,
1,1,2‐tri‐,
1,1,2,2‐tetra‐borylated
cyclobutanes.
In
fact,
these
compounds
belong
family
that
presently
lacks
synthetic
pathways.
Interestingly,
when
α‐methylstyrene
was
used,
reaction
involves
an
interesting
1,5‐hydrogen
atom
transfer
(HAT).
Mechanistic
deuterium‐labeling
studies
have
provided
insight
into
outcome
process.
addition,
cyclobutanes
then
demonstrated
useful
selective
oxidation
processes
resulting
cyclobutanones
γ‐lactones.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Сен. 14, 2023
In
recent
years,
numerous
1,2-R
shift
(R
=
aliphatic
or
aryl)
based
on
tetracoordinate
boron
species
have
been
well
investigated.
the
contrary,
corresponding
radical
migrations,
especially
1,2-boryl
for
construction
of
organoborons
is
still
in
its
infancy.
Given
paucity
and
significance
such
strategies
chemistry,
it
urgent
to
develop
other
efficient
alternative
synthetic
protocols
enrich
these
underdeveloped
1,2-boron
before
their
fundamental
potential
applications
could
be
fully
explored
at
will.
Herein,
we
demonstrated
a
visible-light-induced
photoredox
neutral
decarboxylative
cross-coupling
reaction,
which
undergoes
give
translocated
C-radical
further
capture
versatile
acceptors.
The
mild
reaction
conditions,
good
functional-group
tolerance,
broad
β-boryl
NHPI
esters
scope
as
acceptors
make
this
protocol
applicable
modification
bioactive
molecules.
It
can
expected
that
methodology
will
very
useful
tool
an
strategy
primary
via
novel
mode.
Chemical Science,
Год журнала:
2024,
Номер
15(11), С. 4031 - 4040
Опубликована: Янв. 1, 2024
A
free-radical
approach
featuring
an
intramolecular
aryl
migration
has
significantly
expanded
the
scope
for
alkyl–(hetero)arylation
of
simple
olefins.
It
was
also
leveraged
as
key
step
in
a
new
synthesis
recently
approved
pharmaceutical.
Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
364(8), С. 1388 - 1393
Опубликована: Фев. 23, 2022
Abstract
A
photoredox
catalyzed
trifluoromethyl
radical‐triggered
trifunctionalization
of
5‐hexenenitriles
via
cyano
group
migration
is
reported.
The
high
chemo‐selectivity
even
in
the
presence
aryl
or
heteroaryl
groups
as
competitors.
This
protocol
provides
a
facile
access
to
broad
scope
CF
3
‐containing
compounds
with
molecular
complexity
and
functional
diversity.
success
gram‐scale
reaction
versatility
products
derivative
synthesis
illustrate
potential
value
this
transformation
synthetic
chemistry.
magnified
image
Green Chemistry,
Год журнала:
2022,
Номер
24(16), С. 6138 - 6144
Опубликована: Янв. 1, 2022
With
key
steps
involving
electro-oxidation-triggered
Smiles-type
radical
rearrangement
and
chemical
reduction
with
SO
2
,
a
formal
redox-neutral
electrosynthesis
for
migratory
heteroaryltrifluoromethylation
of
allylic
amines
was
developed.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(26)
Опубликована: Апрель 22, 2023
Twofold
distal
C-H
functionalization
was
accomplished
by
difunctionalization
of
nonactivated
alkenes
to
provide
rapid
access
multifunctionalized
molecules.
The
multicomponent
ruthenium-catalyzed
remote
1,n-difunctionalization
(n=6,7)
with
fluoroalkyl
halides
and
heteroarenes
in
a
modular
manner
is
reported.
meta-C(sp2
)-H/C-6(sp3
)-H
featured
mild
conditions,
unique
selectivity,
broad
substrate
scope
domino
process
for
twofold
C(sp2
)-H/C(sp3
activation
the
sequential
formation
three
different
carbon-centered
radicals.
A
plausible
mechanism
proposed
based
on
detailed
experimental
computational
studies.
Organic Letters,
Год журнала:
2024,
Номер
26(15), С. 3213 - 3217
Опубликована: Апрель 4, 2024
With
in-depth
research
on
1,2-difunctionalization,
remote
difunctionalization
has
garnered
widespread
attention
for
achieving
multifunctionality.
Herein,
we
report
a
strategy
under
mild
conditions.
This
exhibited
good
substrate
suitability
and
functional
group
tolerance.
In
addition,
the
significance
of
this
method
is
further
evidenced
by
its
successful
application
in
scaling
up
conducting
additional
transformations
target
compounds.
Mechanistic
studies
showed
that
radical
might
be
involved
process.
Chemical Communications,
Год журнала:
2021,
Номер
58(7), С. 1005 - 1008
Опубликована: Дек. 15, 2021
A
novel
radical-mediated
trifunctionalization
of
hexenenitriles
via
the
strategy
remote
functional
group
migration
is
disclosed.
portfolio
functionalized
are
employed
as
substrates.
After
difunctionalization
unactivated
alkenyl
part
cyano
migration,
in
situ
formed
radical
intermediate
captured
by
an
azido
radical,
thus
enabling
trifunctionalization.
The
reaction
features
mild
conditions
and
broad
compatibility,
leading
to
valuable
products
bearing
multiple
useful
groups.
This
protocol
further
extends
scope
migration.
