Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(18), P. 3972 - 3976
Published: April 25, 2024
Facile
access
to
sp3-rich
scaffolds
containing
a
sulfonyl
fluoride
group
is
still
limited.
Herein,
we
describe
mild
and
scalable
strategy
for
the
preparation
of
alkyl
fluorides
from
readily
available
bromides
alcohols
using
photoredox
catalysis.
This
approach
based
on
halogen
atom
transfer
(XAT),
followed
by
SO2
capture
fluorination.
The
method
features
conditions
enabling
fast
high-value
derivatives
has
been
scaled
up
5
g
continuous
stirred
tank
reactor
cascade.
Accounts of Chemical Research,
Journal Year:
2022,
Volume and Issue:
55(17), P. 2526 - 2541
Published: Aug. 20, 2022
ConspectusA
radical
shift
toward
energy
transfer
photocatalysis
from
electron
under
visible-light
photoirradiation
is
often
due
to
the
greener
prospects
of
atom
and
process
economy.
Recent
advances
in
embrace
unique
strategies
for
direct
small-molecule
activation
sometimes
extraordinary
chemical
bond
formation
absence
additional/sacrificial
reagents.
Selective
requires
careful
selection
substrates
photocatalysts
a
perfect
match
with
respect
their
triplet
energies
while
having
incompatible
redox
potentials
prevent
competitive
pathways.
Substrates
containing
labile
N–O
bonds
are
potential
targets
generating
reactive
key
intermediates
via
access
variety
functionalized
molecules.
Typically,
differential
densities
N
O
heteroatoms
have
been
exploited
generation
either
N-
or
O-centered
by
pathway.
However,
latest
developments
involve
homolysis
generate
both
radicals
subsequent
utilization
diverse
organic
transformations,
also
sacrificial
In
this
Account,
we
highlight
our
contributions
field
intermediates,
coverage
useful
mechanistic
insights.
More
specifically,
well-designed
bond-containing
such
as
1,2,4-oxadiazolines,
oxime
esters,
N-indolyl
carbonates,
N-enoxybenzotriazoles
were
successfully
utilized
versatile
transformations
involving
selective
over
high
state
energy.
Direct
N-,
O-,
C-centered
(if
decarboxylation
follows)
was
achieved
cross-couplings
rearrangement
processes.
particular,
open-shell
nitrogen
including
N(sp2)
N(sp3)
nitrenes,
utilized.
Notably,
diversified
identical
through
control
reaction
conditions.
1,2,4-Oxadiazolines
converted
into
spiro-azolactams
iminyl
presence
1O2,
benzimidazoles,
sulfoximines
external
sulfoxide
reagent
nitrene
inert
Besides,
esters
underwent
intramolecular
C(sp3)–N
radical–radical
coupling
intermolecular
combined
transfer–hydrogen
strategy.
Furthermore,
series
electrochemical
photophysical
experiments
well
computational
studies
performed
substantiate
proposed
energy-transfer-driven
We
hope
that
Account
will
serve
guide
rational
design
processes
further
bonds.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(4), P. 2364 - 2374
Published: Jan. 18, 2023
Sulfur(VI)
fluoride
exchange
(SuFEx)
gives
rise
to
a
plethora
of
high-valent
sulfur
linkages;
however,
the
availability
(aliphatic)
sulfonyl
manifolds
lag
behind,
owing
limited
sources
introducing
SO2F
moiety
via
classical
two-electron
approach.
Recently,
radical-based
methodologies
have
emerged
as
complementary
strategy
increase
diversity
accessible
click
partners.
In
this
work,
synthesis
bench-stable
sulfamoyl
reagent
is
presented,
which
may
undergo
sigma-bond
homolysis
upon
visible-light-induced
sensitization
form
protected
β-amino
fluorides
from
alkene
feedstocks.
Notably,
offers
an
appealing
access
various
building
blocks
for
peptido
fluorides,
relevant
in
medicinal
chemistry
context,
well
intriguing
entry
β-ammonium
sulfonates
and
β-sultams,
alkenes.
Densely
functionalized
1,3-sultones
were
obtained
by
employing
allyl
alcohols
substrates.
Surprisingly,
chloride-derived
β-imino
underwent
S-O
bond
formation
ring
closure
yield
rigid
cyclopropyl
sulfonate
ester
under
SuFEx
conditions.
Furthermore,
engaging
thiol-based
hydrogen
atom
donor
reaction,
reactivity
same
can
be
tuned
toward
direct
aliphatic
fluorides.
Mechanistic
experiments
indicate
energy
transfer
(EnT)-mediated
process.
The
transient
radical
adds
product
occurs
either
radical-radical
coupling
or
(HAT),
respectively.
National Science Review,
Journal Year:
2023,
Volume and Issue:
10(6)
Published: April 29, 2023
Abstract
Sulfur
fluoride
exchange
(SuFEx),
a
new
generation
of
click
chemistry,
was
first
presented
by
Sharpless,
Dong
and
co-workers
in
2014.
Owing
to
the
high
stability
yet
efficient
reactivity
SVI–F
bond,
SuFEx
has
found
widespread
applications
organic
synthesis,
materials
science,
chemical
biology
drug
discovery.
A
diverse
collection
linkers
emerged,
involving
gaseous
SO2F2
SOF4
hubs;
SOF4-derived
iminosulfur
oxydifluorides;
O-,
N-
C-attached
sulfonyl
fluorides
sulfonimidoyl
fluorides;
novel
sulfondiimidoyl
fluorides.
This
review
summarizes
progress
these
connectors,
with
an
emphasis
on
analysing
advantages
disadvantages
synthetic
strategies
connectors
based
concept,
it
is
expected
be
beneficial
researchers
rapidly
correctly
understand
this
field,
thus
inspiring
further
development
chemistry.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(39)
Published: Aug. 9, 2022
Abstract
Recently,
radical
fluorosulfonylation
is
emerging
as
an
appealing
approach
for
the
synthesis
of
sulfonyl
fluorides,
which
are
highly
in
demand
various
disciplines,
particularly
chemical
biology
and
drug
discovery.
Here,
we
report
first
establishment
hydro‐fluorosulfonylation
alkenes,
enabled
by
using
1‐fluorosulfonyl
2‐aryl
benzoimidazolium
(FABI)
effective
redox‐active
precursor.
This
method
provides
a
new
facile
aliphatic
fluorides
from
unactivated
can
be
further
applied
to
late‐stage
modifications
natural
products
peptides,
well
ligation
drugs
combination
with
click
chemistry.
Remarkably,
this
system
could
enable
alkynes,
affording
valuable
alkenylsulfonyl
fluoride
rare,
high
Z
‐selectivity,
normally
less
stable
more
challenging
synthesize
comparison
E
‐configured
products.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(6), P. 3668 - 3675
Published: Feb. 28, 2023
Sulfonyl
fluorides
are
highly
versatile
molecules
for
click
chemistry
that
have
found
applications
in
many
areas
of
and
biology.
Recent
chemical
approaches
focused
on
the
synthesis
alkyl
sulfonyl
from
readily
available
starting
materials.
Here,
we
report
a
photocatalytic
organotrifluoroborates
boronic
acid
pinacol
esters,
which
building
blocks
commonly
employed
by
medicinal
chemists
bioactive
molecules.
Steady-state
time-resolved
spectroscopy
confirmed
absorption
photons
acridinium
catalysts
leads
to
oxidation
organotrifluoroborate
substrates.
The
reaction
exhibits
broad
functional
group
tolerance,
can
be
attributed
mild
activation
with
visible
light.
Importantly,
this
general
approach
provides
easy
access
primary,
secondary,
tertiary
fluorides.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(12), P. 2381 - 2386
Published: March 15, 2024
Organic
sulfones
are
an
important
class
of
chemical
compounds
widely
used
in
many
research
fields.
The
direct
decarboxylative
sulfonylation
carboxylic
acids
is
attractive
but
challenging,
particularly
when
iron
as
a
metal
catalyst.
Herein,
we
describe
photoinduced
iron-catalytic
method
for
the
synthesis
directly
using
via
radical-based
decarboxylation.
This
protocol
mild,
highly
efficient,
and
easy-to-operate.
A
broad
scope
carbon
electrophiles
could
be
well
tolerated.
mechanism
involving
iron-catalyzed
decarboxylation,
radical
transfer,
single-electron
reduction,
nucleophilic
attack
proposed.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(3), P. 713 - 718
Published: Jan. 12, 2024
Sulfonamides
are
important
structures
in
pharmaceuticals,
agrochemicals,
and
organocatalysts,
yet
the
rapid
benign
synthesis
of
these
compounds
is
still
a
great
challenge.
Herein
we
report
photoinduced
method
for
synthesizing
sulfonamides
from
(hetero)aryl
carboxylic
acid
oxime
esters.
This
reaction
proceeds
via
one-pot
cascade
radical–radical
cross-coupling
by
energy-transfer-mediated
photocatalysis.
A
wide
substrate
scope
including
substrates
late-stage
modification
pharmaceutical
molecular
entities
reveal
its
generality.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(6), P. 4318 - 4328
Published: March 6, 2024
Sulfonyl
fluorides
have
found
increasing
applications
as
functional
molecules
in
chemistry
and
biology.
We
herein
report
a
copper-catalyzed
atom-economical
access
to
two
categories
of
sulfonyl
through
radical
relay
strategy
the
presence
an
SO2
surrogate.
The
aliphatic
C(sp3)–H
bond
N-fluoro-N-alkyl
sulfonamides
reacted
via
1,5-hydrogen
atom
transfer
(HAT)
process,
affording
alkanesulfonyl
with
proximal
amino
group.
On
other
hand,
utilizing
substrates
containing
proper
C═C
double
resulted
intramolecular
olefin
aminofluorosulfonylation,
allowing
synthesis
fluorosulfonyl-functionalized
pyrrolidines
piperidines
atom-transfer
addition
(ATRA).
Both
reaction
systems
proceeded
under
mild
conditions,
requiring
no
additional
fluorine
source.
Experimental
computational
studies
suggest
that
S–F
coupling
is
likely
achieved
radical-rebound
pathway.
By
taking
advantage
SuFEx
multifunctionality
products,
method
applicable
late-stage
modification
bioactive
compounds,
drug
ligation
chemistry,
organic
synthesis.