Organic Letters,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Dec. 4, 2024
Nitrogen
central
radicals
(NCRs)
are
versatile
synthetic
intermediates
for
creating
functional
nitrogen-containing
molecules.
Herein,
a
photosensitized
β-sulfonylamination
of
terminal
alkynes
as
well
acetylene
has
been
established
by
employing
N-sulfonyl
heteroaromatics
bifunctional
reagents
(BFRs)
to
efficiently
deliver
(E)-β-sulfonylvinylamines
with
excellent
regio-
and
stereoselectivities.
Mechanistic
studies
suggest
base-accelerated
energy
transfer
(EnT)
photocatalysis
involving
aromatic
NCR
formation,
radical
addition
alkynes,
sulfonylation
processes.
ACS Catalysis,
Journal Year:
2025,
Volume and Issue:
15(3), P. 1854 - 1941
Published: Jan. 17, 2025
Over
the
past
decade,
visible-light-mediated
energy-transfer
(EnT)
catalysis,
particularly
triplet–triplet
(TTEnT)
has
emerged
as
a
mild
and
environmentally
friendly
approach
for
diverse
organic
synthetic
transformations.
In
contrast
to
photoredox
which
typically
requires
sacrificial
electron
donors
or
acceptors
complete
catalytic
cycle,
EnT
photocatalysis
generally
proceeds
with
high
atom
economy
while
minimizing
generation
of
wasteful
byproducts.
Furthermore,
successful
catalysis
is
contingent
upon
precise
control
redox
potentials
both
photocatalysts
substrates,
strategies
are
primarily
influenced
by
triplet
energy
compatibility
between
these
entities.
Considering
growing
importance
photocatalysis,
well
hydrofunctionalization
difunctionalization
reactions
in
synthesis,
this
review
systematically
summarizes
significant
advancements
EnT-enabled
unsaturated
compounds
via
sigma-bond
homolysis
over
decade.
Special
emphasis
placed
on
elucidating
substrate
scopes
mechanistic
scenarios.
Additionally,
discusses
versatile
applications
methodologies
addresses
current
challenges
opportunities
within
evolving
research
field.
This
structured
into
six
main
categories
based
different
types
sigma-bonds
undergoing
homolysis.
These
include
transformations
mediated
1)
N–O
bond
oxime
esters
other
N,O-radical
precursors;
2)
N–S
N-sulfonyl
imines
N,S-radical
3)
chalcogen–chalcogen
disulfides
oxy/thio/selenosulfonates;
4)
C–S
tri/difluoromethylated
sulfinates,
acetylenic
triflones,
arylsulfonium
salts;
5)
C–X
(X
=
halogen)
halides;
6)
acceptors.
Through
providing
theoretical
backgrounds
along
comprehensive
overview
currently
employed
acceptors,
photosensitizers,
contemporary
EnT-induced
compounds,
aims
serve
an
invaluable
resource
future
innovations
rapidly
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(43), P. 23814 - 23823
Published: Oct. 18, 2023
Radical
remote
1,n-difunctionalization
reactions
(n
>
2)
of
alkenes
are
powerful
tools
to
efficiently
introduce
functional
groups
with
selected
distances
into
target
molecules.
Among
these
reactions,
1,5-difunctionalizations
an
important
subclass,
leading
sought-after
scaffolds,
but
typically
suffer
from
tailored
starting
materials
and
strict
limitations
for
the
formed
group
in
2-position.
Seeking
address
issues
make
radical
more
applicable,
we
report
a
novel
three-component
1,2,5-trifunctionalization
reaction
between
imine-based
bifunctional
reagents
two
distinct
alkenes,
driven
by
visible
light
energy
transfer-catalysis.
Key
achieving
this
selective
one-step
installation
three
different
via
choreographed
formation
four
bonds
was
utilization
1,2-boron
shift
rigorous
capitalization
polarities
stabilities.
Thorough
mechanistic
studies
were
carried
out,
synthetic
utility
obtained
products
demonstrated
various
downstream
modifications.
Notably,
addition
functionalization
individual
groups,
their
interplay
gave
rise
unique
array
cyclic
products.
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.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 17, 2025
A
metal-free
photosensitized
1,2-imino-thiocyanation
of
olefins
has
been
established
by
using
the
easily
accessible
bifunctional
reagent
S-cyano-N-(diphenylmethylene)
thiohydroxylamine.
wide
range
were
successfully
transformed
into
corresponding
β-iminothiocyanates
in
moderate
to
high
yields.
This
protocol
stands
out
for
its
nature,
broad
substrate
compatibility,
and
atom
step
economy,
providing
an
effective
strategy
assembling
β-amino
thiocyanate-containing
scaffolds.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(10), P. 2108 - 2113
Published: March 5, 2024
A
metal-free
photosensitized
1,2-imino-sulfamoylation
of
olefins
by
employing
a
tailor-made
sulfamoyl
carbamate
as
the
difunctionalization
reagent
has
been
established.
This
protocol
exhibits
versatility
across
broad
substrate
scope,
including
aryl
and
aliphatic
alkenes,
leading
to
synthesis
diverse
β-imino
sulfonamides
in
moderate
good
yields.
method
is
characterized
its
reaction
system,
mild
conditions,
excellent
regioselectivity,
high
atom
economy,
serving
promising
platform
for
preparation
β-amino
sulfonamide-containing
molecules,
particularly
context
drug
discovery.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(44)
Published: July 22, 2024
Sulfur(VI)-based
functional
groups
are
popular
scaffolds
in
a
wide
variety
of
research
fields
including
synthetic
and
medicinal
chemistry,
as
well
chemical
biology.
The
growing
interest
sulfur(VI)-containing
molecules
has
motivated
the
scientific
community
to
explore
new
methods
synthesize
modify
them.
Here,
photocatalysis
plays
key
role
granting
access
types
reactivity
under
mild
reaction
conditions.
In
this
Perspective,
we
present
selection
works
reported
last
six
years
focused
on
photocatalytic
assembly
sulfones,
sulfonamides,
sulfoximines.
We
addressed
intermediates
for
each
transformation,
while
discussing
limitations
strength
points
protocols.
Future
directions
field
finally
presented.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(22), P. 6340 - 6346
Published: Jan. 1, 2024
We
developed
the
first
transition-metal-catalyzed,
regiodivergent
sulfonylation
of
aziridines,
enabling
efficient
synthesis
diverse
β-amino
sulfones
under
mild
conditions
with
broad
substrate
compatibility
and
high
regioselectivity.
ChemistrySelect,
Journal Year:
2024,
Volume and Issue:
9(43)
Published: Nov. 1, 2024
Abstract
Herein,
we
developed
a
metal‐free,
photosensitized
strategy
for
difunctionalization
of
olefin
feedstocks
to
access
β‐amino
sulphone
architectures,
enabled
by
tailor‐made,
readily
accessible
sulfonylamide
bifunctional
reagent.
This
protocol
could
accommodate
wide
range
alkenes
and
variety
sulfonylamides,
with
high
yields
excellent
regioselectivity.
Given
remarkably
mild
reaction
conditions,
starting
materials,
functional
group
tolerance,
well‐defined
regioselectivity,
this
approach
would
enable
an
efficient
platform
the
assembly
densely
functionalized
molecular
scaffolds.
