Abstract
Sulfur(VI)
fluoride
exchange
(SuFEx)
chemistry
that
relies
on
the
unique
reactivity–stability
balance
of
high
valent
organosulfur
has
emerged
as
a
promising
topic
for
next-generation
click
reaction.
Sulfonyl
fluorides
are
most
widely
used
connective
hubs
SuFEx
reaction
with
widespread
applications
in
fields
chemical
biology,
drug
discovery,
and
materials
science.
Compared
current
methods,
direct
fluorosulfonylation
fluorosulfonyl
radicals
concise
efficient
approach
production
sulfonyl
fluorides.
The
highly
active
SO2F
radical
was
an
unstable
inaccessible
precursor
until
it
observed
decomposition
azide,
which
inspired
efforts
towards
precursors
processes.
This
review
presents
discusses
breakthroughs
generation
from
various
precursors,
well
their
application
synthesis
diverse
functionalized
1
Introduction
2
FSO2Cl
Radical
Precursor
3
Benzimidazolium
Fluorosulfonates
Precursors
4
Alk-1-ynylsulfonyl
Fluorides
5
(Diarylmethylene)sulfamoyl
6
Vinyl
Fluorosulfates
7
Conclusion
Outlook
Angewandte Chemie,
Год журнала:
2024,
Номер
136(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
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 27, 2024
Abstract
Aminoarenes
are
important
molecules
for
broad
applications
in
nearly
all
modern
industries
that
involve
chemicals.
Direct
and
site‐selective
C−H
bond
amination
of
arenes
provides
the
most
efficient
convenient
method
to
prepare
aminoarenes.
A
main
challenge
is
selectively
install
amino
group
(or
other
functional
groups)
distal
para‐
carbon
(especially
multi‐substituted
arenes)
during
functionalization
events.
Herein,
we
address
this
problem
by
designing
a
new
strategy
via
sequential
radical
dearomatization/radical
amination/rearomatization
process
para
‐selective
benzyl
alcohols.
The
‐selectivity
our
reaction
completely
independent
electronic
steric
properties
substituents
arene
substrates.
with
many
(up
full
substitution)
diverse
substitution
patterns,
including
those
difficult
synthesize
previously,
could
be
readily
prepared
using
protocols.
Further
exploration
current
shall
lead
challenging
arenes.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(43)
Опубликована: Июль 27, 2024
Abstract
Aminoarenes
are
important
molecules
for
broad
applications
in
nearly
all
modern
industries
that
involve
chemicals.
Direct
and
site‐selective
C−H
bond
amination
of
arenes
provides
the
most
efficient
convenient
method
to
prepare
aminoarenes.
A
main
challenge
is
selectively
install
amino
group
(or
other
functional
groups)
distal
para‐
carbon
(especially
multi‐substituted
arenes)
during
functionalization
events.
Herein,
we
address
this
problem
by
designing
a
new
strategy
via
sequential
radical
dearomatization/radical
amination/rearomatization
process
para
‐selective
benzyl
alcohols.
The
‐selectivity
our
reaction
completely
independent
electronic
steric
properties
substituents
arene
substrates.
with
many
(up
full
substitution)
diverse
substitution
patterns,
including
those
difficult
synthesize
previously,
could
be
readily
prepared
using
protocols.
Further
exploration
current
shall
lead
challenging
arenes.
Abstract
Sulfur(VI)
fluoride
exchange
(SuFEx)
chemistry
that
relies
on
the
unique
reactivity–stability
balance
of
high
valent
organosulfur
has
emerged
as
a
promising
topic
for
next-generation
click
reaction.
Sulfonyl
fluorides
are
most
widely
used
connective
hubs
SuFEx
reaction
with
widespread
applications
in
fields
chemical
biology,
drug
discovery,
and
materials
science.
Compared
current
methods,
direct
fluorosulfonylation
fluorosulfonyl
radicals
concise
efficient
approach
production
sulfonyl
fluorides.
The
highly
active
SO2F
radical
was
an
unstable
inaccessible
precursor
until
it
observed
decomposition
azide,
which
inspired
efforts
towards
precursors
processes.
This
review
presents
discusses
breakthroughs
generation
from
various
precursors,
well
their
application
synthesis
diverse
functionalized
1
Introduction
2
FSO2Cl
Radical
Precursor
3
Benzimidazolium
Fluorosulfonates
Precursors
4
Alk-1-ynylsulfonyl
Fluorides
5
(Diarylmethylene)sulfamoyl
6
Vinyl
Fluorosulfates
7
Conclusion
Outlook
