ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(22), P. 14503 - 14512
Published: Oct. 27, 2023
Sulfur(VI)
fluoride
exchange
(SuFEx)
click
chemistry
provides
a
powerful
tool
for
the
rapid
assembly
of
modular
connections.
Herein,
we
report
an
organocatalytic
SuFEx
reaction
sulfonyl
fluorides,
fluorosulfates,
and
sulfamoyl
fluorides.
Under
catalysis
10
mol
%
N-heterocyclic
carbene
(NHC),
or
under
relay
NHC
HOBt,
different
SuFExable
hubs
efficiently
undergo
reactions
with
alcohols
amines
to
afford
sulfonates,
sulfonamides,
sulfates,
sulfamates,
sulfamides
in
49–99%
yields.
More
than
190
sulfonylated
products,
including
25
natural
product
derivatives,
have
been
prepared
through
this
method.
Mechanism
study
showed
that
NHCs
might
act
as
carbon-centered
Broønsted
base
activate
formation
hydrogen
bonding.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(50)
Published: Oct. 18, 2022
Abstract
The
sulfur
fluoride
exchange
(SuFEx)
reaction
is
significant
in
drug
discovery,
materials
science,
and
chemical
biology.
Conventionally,
it
involves
installation
of
SO
2
F
followed
by
a
catalyst.
We
report
catalyst‐free
Aza‐Michael
addition
to
install
then
SuFEx
with
amines,
both
occurring
concert,
microdroplets
under
ambient
conditions.
microdroplet
accelerated
factor
∼10
4
relative
the
corresponding
bulk
reaction.
suggest
that
superacidic
surface
assists
protonating
fluorine
create
good
leaving
group.
scope
was
established
performing
individual
reactions
18
amines
four
solvents
confirmed
using
high‐throughput
desorption
electrospray
ionization
experiments.
study
demonstrates
value
microdroplet‐assisted
combination
experimentation
for
characterization
scope.
Proceedings of the National Academy of Sciences,
Journal Year:
2022,
Volume and Issue:
119(37)
Published: Sept. 7, 2022
Diversity
Oriented
Clicking
(DOC)
is
a
discovery
method
geared
toward
the
rapid
synthesis
of
functional
libraries.
It
combines
best
attributes
both
classical
and
modern
click
chemistries.
DOC
strategies
center
upon
chemical
diversification
core
"SuFExable"
hubs-exemplified
by
2-Substituted-Alkynyl-1-Sulfonyl
Fluorides
(SASFs)-enabling
modular
assembly
compounds
through
multiple
reaction
pathways.
We
report
here
range
stereoselective
Michael-type
addition
pathways
from
SASF
hubs
including
reactions
with
secondary
amines,
carboxylates,
1
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Aug. 24, 2023
Sulfonyl
and
sulfonimidoyl
fluorides
are
versatile
substrates
in
organic
synthesis
medicinal
chemistry.
However,
they
have
been
exclusively
used
as
S(VI)+
electrophiles
for
defluorinative
ligations.
Converting
sulfonyl
to
S(VI)
radicals
is
challenging
underexplored
due
the
strong
bond
dissociation
energy
of
SVI-F
high
reduction
potentials,
but
once
achieved
would
enable
dramatically
expanded
synthetic
utility
downstream
applications.
In
this
report,
we
disclose
a
general
platform
address
issue
through
cooperative
organosuperbase
activation
photoredox
catalysis.
Vinyl
sulfones
sulfoximines
obtained
with
excellent
E
selectivity
under
mild
conditions
by
coupling
reactions
alkenes.
The
method
preparation
functional
polymers
dyes
also
demonstrated.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(22), P. 14503 - 14512
Published: Oct. 27, 2023
Sulfur(VI)
fluoride
exchange
(SuFEx)
click
chemistry
provides
a
powerful
tool
for
the
rapid
assembly
of
modular
connections.
Herein,
we
report
an
organocatalytic
SuFEx
reaction
sulfonyl
fluorides,
fluorosulfates,
and
sulfamoyl
fluorides.
Under
catalysis
10
mol
%
N-heterocyclic
carbene
(NHC),
or
under
relay
NHC
HOBt,
different
SuFExable
hubs
efficiently
undergo
reactions
with
alcohols
amines
to
afford
sulfonates,
sulfonamides,
sulfates,
sulfamates,
sulfamides
in
49–99%
yields.
More
than
190
sulfonylated
products,
including
25
natural
product
derivatives,
have
been
prepared
through
this
method.
Mechanism
study
showed
that
NHCs
might
act
as
carbon-centered
Broønsted
base
activate
formation
hydrogen
bonding.
