ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(5), P. 3115 - 3127
Published: Feb. 13, 2024
Although
the
transition
metal-catalyzed
radical
fluorine
atom
transfer
(FAT)
strategy
has
emerged
as
a
powerful
tool
for
construction
of
C–F
bonds,
to
our
knowledge,
this
approach
rarely
been
applied
formation
S–F
bonds.
Here,
we
report
that
4-methoxypyridine
1-oxide
can
serve
an
inexpensive
and
simple
yet
effective
ligand
thus
promote
transformation
copper-mediated
challengeable
FAT
sulfonyl
radicals,
paving
way
assembly
FSO2
group.
Based
on
concept,
three
Cu(I)-catalyzed
protocols
involving
site-selective
intra-
intermolecular
fluorosulfonylation
inert
C(sp3)–H
bonds
1,2-aminofluorosulfonylation
inactivated
alkenes
have
developed,
enabling
preparation
C(sp3)-rich
aliphatic
fluorides
cannot
be
easily
synthesized
by
known
methods.
These
practical
operationally
methods
result
in
high
functional
group
tolerance
under
mild
conditions
modification
bioactive
derivatives
highly
valued
molecules.
Detailed
mechanistic
studies
indicate
unique
role
facilitating
such
rare
FATs
via
outer-sphere
pathway.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
11(1), P. 217 - 235
Published: Nov. 14, 2023
This
review
summarizes
the
latest
achievements
in
photochemical
and
electrochemical
strategies
for
synthesis
of
sulfonyl
fluorides
focuses
on
novel
features
proposed
mechanisms.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(46), P. 13384 - 13391
Published: Jan. 1, 2023
Sulfinamides
are
some
of
the
most
centrally
important
four-valent
sulfur
compounds
that
serve
as
critical
entry
points
to
an
array
emergent
medicinal
functional
groups,
molecular
tools
for
bioconjugation,
and
synthetic
intermediates
including
sulfoximines,
sulfonimidamides,
sulfonimidoyl
halides,
well
a
wide
range
other
S(iv)
S(vi)
functionalities.
Yet,
accessible
chemical
space
sulfinamides
remains
limited,
approaches
largely
confined
two-electron
nucleophilic
substitution
reactions.
We
report
herein
direct
radical-mediated
decarboxylative
sulfinamidation
first
time
enables
access
from
broad
structurally
diverse
carboxylic
acids.
Our
studies
show
formation
prevails
despite
inherent
thermodynamic
preference
radical
addition
nitrogen
atom,
while
machine
learning-derived
model
facilitates
prediction
reaction
efficiency
based
on
computationally
generated
descriptors
underlying
reactivity.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(7), P. 1410 - 1415
Published: Feb. 15, 2024
A
radical
hydro-fluorosulfonylation
of
propargyl
alcohols
with
FSO2Cl
is
presented
based
on
the
photoactivation
electron
donor–acceptor
(EDA)
complex.
The
reaction
avoids
requirement
for
photocatalysts,
bases,
hydrogen
donor
reagents,
any
other
additives,
and
harsh
conditions,
enabling
facile
synthesis
various
functionalized
γ-hydroxy
(E)-alkenylsulfonyl
fluorides.
These
multifunctional
sulfonyl
fluorides
can
be
further
diversified,
providing
access
to
privileged
molecules
biological
relevance.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(38), P. 7051 - 7056
Published: Sept. 20, 2023
In
this
report,
we
present
a
photocatalytic
ring-opening
fluorosulfonylation
of
strained
cycloalkanols
with
sulfur
dioxide
and
NFSI
under
mild
conditions
for
the
synthesis
carbonyl-containing
aliphatic
sulfonyl
fluorides.
The
synthetic
potential
fluoride
products
has
been
examined
by
diverse
transformations,
including
SuFEx
reactions
Baeyer-Villiger
oxidation
reactions.
Mechanistic
studies
demonstrate
that
reaction
operates
through
radical
C-C
bond
cleavage/SO2
insertion/fluorination
cascade
process.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(21), P. 3910 - 3915
Published: May 24, 2023
An
efficient
aminofluorosulfonylation
strategy
was
developed
for
the
synthesis
of
various
pyrazoline-functionalized
aliphatic
sulfonyl
fluorides
using
β,γ-unsaturated
hydrazones
with
sulfur
dioxide
and
NFSI
as
starting
materials
under
mild
conditions.
The
fluoride
products
could
be
successfully
transformed
into
corresponding
sulfonate
esters
amides
via
sulfur(VI)
exchange
(SuFEx)
click
reactions.
Preliminary
mechanistic
investigations
demonstrate
that
reaction
operates
through
a
radical
cyclization/SO2
insertion/fluorination
cascade
process.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
We
report
here
a
metal-free,
redox-neutral
photocatalytic
strategy
of
SO
2
gas
functionalization
resulting
in
the
one-pot
synthesis
sulfonamides,
sulfonate
esters,
and
thiosulfonates
through
photoexcited
phenalenyl
(PLY)
ligand.
Chemical Reviews,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 22, 2025
Fluorine
and
nitrogen
form
a
successful
partnership
in
organic
synthesis,
medicinal
chemistry,
material
sciences.
Although
fluorine-nitrogen
chemistry
has
long
rich
history,
this
field
received
increasing
interest
made
remarkable
progress
over
the
past
two
decades,
driven
by
recent
advancements
transition
metal
organocatalysis
photochemistry.
This
review,
emphasizing
contributions
from
2015
to
2023,
aims
update
state
of
art
synthesis
applications
nitrogen-based
organofluorine
functional
molecules
chemistry.
In
dedicated
sections,
we
first
focus
on
fluorine-containing
reagents
organized
according
type
groups
attached
nitrogen,
including
N-F,
N-RF,
N-SRF,
N-ORF.
review
also
covers
nitrogen-linked
building
blocks,
catalysts,
pharmaceuticals,
agrochemicals,
underlining
these
components'
broad
applicability
growing
importance
modern
