Synthesis,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Nov. 11, 2024
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
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(15), P. 10899 - 10907
Published: April 3, 2024
In
the
long-standing
quest
to
synthesize
fundamental
building
blocks
with
key
functional
group
motifs,
photochemistry
in
recent
past
has
comprehensively
established
its
attractiveness.
Amino
alcohols
are
not
only
functionally
diverse
but
ubiquitous
biologically
active
realm
of
compounds.
We
developed
bench-stable
bifunctional
reagents
that
could
then
access
sparsely
reported
γ-amino
directly
from
feedstock
alkenes
through
energy
transfer
(EnT)
photocatalysis.
A
designed
1,3-linkage
across
is
made
possible
by
intervention
a
radical
Brook
rearrangement
takes
place
downstream
EnT-mediated
homolysis
our
reagent(s).
combination
experimental
mechanistic
investigations
and
detailed
computational
studies
(DFT)
indicates
chain
propagated
reaction
pathway.
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
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(25)
Published: April 11, 2024
Abstract
While
polyborylated
alkenes
are
being
recognized
for
their
elevated
status
as
highly
valuable
reagents
in
modern
organic
synthesis,
allowing
efficient
access
to
a
diverse
array
of
transformations,
including
the
formation
C−C
and
C‐heteroatom
bonds,
potential
energy‐transfer
reactive
groups
has
remained
unexplored.
Yet,
this
holds
key
generating
elusive
biradical
species,
which
can
be
captured
by
olefins,
thereby
leading
construction
new
highly‐borylated
scaffolds.
Herein,
we
report
designed
strategy
photosensitized
[2+2]‐cycloadditions
poly‐borylated
with
various
olefins
enabling
regioselective
synthesis
cyclobutane
motifs,
1,1‐di‐,
1,1,2‐tri‐,
1,1,2,2‐tetra‐borylated
cyclobutanes.
In
fact,
these
compounds
belong
family
that
presently
lacks
synthetic
pathways.
Interestingly,
when
α‐methylstyrene
was
used,
reaction
involves
an
interesting
1,5‐hydrogen
atom
transfer
(HAT).
Mechanistic
deuterium‐labeling
studies
have
provided
insight
into
outcome
process.
addition,
cyclobutanes
then
demonstrated
useful
selective
oxidation
processes
resulting
cyclobutanones
γ‐lactones.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(17), P. 13343 - 13351
Published: Aug. 22, 2024
Atomic
carbon
and
its
corresponding
masked
analogues
are
exceedingly
underexplored
intermediates
in
synthesis.
Despite
this,
these
reagents
possess
inimitable
reactivity
such
as
the
ability
to
directly
insert
atoms
into
aromatic
frameworks
while
simultaneously
generating
an
additional
bond
at
center
further
diversify
structure.
Herein,
we
report
design
of
orthogonally
reactive
atomic
equivalent
Cl-DADO
demonstrate
application
molecular
editing
indole
pyrrole,
accessing
linchpin-containing
ring-expanded
heterocycles
that
can
be
subsequently
derivatized.
The
value
this
approach
broad
applicability
reagent
highlighted
by
late-stage
skeletal
numerous
natural
products
drug
molecules.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(31), P. 12398 - 12409
Published: Jan. 1, 2024
The
philicity-regulation
and
PCET
mechanism
of
tether-tunable
distonic
radical
anion-mediated
generation
heteroatom-centered
radicals
has
been
explored
via
experimental
theoretical
investigations.
Science Advances,
Journal Year:
2024,
Volume and Issue:
10(30)
Published: July 24, 2024
The
transformation
of
organoboron
compounds
plays
an
important
role
in
synthetic
chemistry,
and
recent
advancements
boron-migration
reactions
have
garnered
considerable
attention.
Here,
we
report
unprecedented
1,2-boron
migrative
acylation
upon
photocatalysis-facilitated
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(30), P. 6396 - 6401
Published: July 24, 2024
Spirocyclobutyl
oxindoles
have
garnered
substantial
attention
in
drug
discovery
and
pharmaceuticals
owing
to
their
wide
range
of
biological
activities.
Strain-release
small-ring
compounds
is
a
powerful
strategy
enable
efficient
access
complex
molecules.
In
this
study,
we
successfully
realized
photoredox-catalyzed
strain-release
radical
spirocyclization
approach
attain
functionalized
spirocyclobutyl
oxindoles.
A
diverse
array
radicals,
such
as
sulfonyl,
phosphonyl,
trifluoromethyl,
were
added
efficiently
the
strained
C-C
σ-bond
bicyclobutanes
(BCBs)
afford
library
Furthermore,
obtained
products
could
be
transformed
into
valuable
building
blocks.
The
observed
reactivity
selectivity
been
rationalized
based
on
density
functional
theory
calculations.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 1, 2025
Radical-mediated
dearomatization
strategies
offer
a
blueprint
for
building
value-added
and
synthetically
valuable
three-dimensional
skeletons
from
readily
available
aromatic
starting
materials.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: April 10, 2025
The
energy
transfer
(EnT)-catalyzed
ring
opening
and
further
decarboxylation
of
isoxazole-5(4H)-ones
enables
the
in
situ
generation
strained
2H-azirines.
Subsequent
selective
C(sp2)-C(sp3)
bond
cleavage
azirine
intermediate
allows
a
formal
[3
+
2]
cycloaddition
with
wide
range
electrophiles,
unlocking
access
to
valuable
pyrroline-type
moieties.
Mechanistic
experiments
combination
density
functional
theory
(DFT)
calculations
revealed
unique
nature
EnT-cascade
process
for
three-membered
aza-cycle
while
providing
insight
into
regio-
diastereoselectivity
annulation.
This
mild
straightforward
method
ensures
rapid
construction
highly
substituted
cyclic
imines,
which
can
be
easily
converted
pyrrolidines,
fused
oxaziridines,
biologically
relevant
β-amino
acid
precursors.