The Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
87(24), P. 16458 - 16472
Published: Nov. 28, 2022
Due
to
the
inert
redox
activity
and
high
triplet
energy,
radical
chemistry
of
1,3-dicarbonyl
compounds
usually
requires
prefunctionalization
substrates,
external
oxidant,
high-energy
UV
light.
Here,
we
report
a
visible-light-driven
photocatalyst/cobaloxime
system
composed
photosensitized
energy
transfer
reaction
(PEnT)
photoinduced
electron
(PET)
with
an
interrupted
6π-photocyclization/dehydrogenative
aromatization
in
one
pot
synthesize
10-phenanthrenols.
Preliminary
mechanistic
studies
revealed
that
fac-Ir(ppy)3
plays
dual
roles
catalysis
for
photocycloaddition
via
1,2-biradical
intermediates
photoredox/cobaloxime
dehydrogenative
1,4-biradical
rather
than
6π
photocyclization
tandem
reaction.
In
contrast
previous
well-established
compounds,
provide
new
strategy
activation
under
visible
light
catalysis,
affording
novel
cyclization
extremely
atom
economy
synthesis
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(11), P. 2830 - 2848
Published: Jan. 1, 2023
Recent
advances
in
the
electrochemical
generation
of
1,3-dicarbonyl
radicals
from
C–H
bonds
and
their
mechanistic
insights
synthetic
applications
have
been
summarized.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(19), P. 13610 - 13621
Published: Sept. 11, 2023
An
electrophilic
spirocyclization
of
N-benzylacrylamides
with
N-halosuccinimides
(NXS)
as
the
halogenating
reagents
has
been
developed.
This
reaction
is
carried
out
at
room
temperature
under
simple
conditions
without
relying
on
metal
reagents,
photochemistry,
or
electrochemistry,
providing
a
fast
and
efficient
route
to
synthesize
wide
variety
4-halomethyl-2-azaspiro[4.5]decanes
satisfactory
yields.
The
approach
further
highlighted
through
gram-scale
synthesis
diverse
transformations
spiro
products.
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(14), P. 3585 - 3590
Published: Jan. 1, 2023
An
organophotoelectrochemical
approach
for
silylation
cyclization
of
CF3-substituted
N
-arylacrylamides
with
organosilanes
under
transition-metal-free
and
oxidant-free
conditions
has
been
developed.
Chemistry - An Asian Journal,
Journal Year:
2023,
Volume and Issue:
18(9)
Published: March 15, 2023
Electrochemical
dearomative
spirocyclization
serves
as
a
green
and
sustainable
approach
to
convert
the
flat,
two-dimension
aromatic
feedstock
into
value-added
three-dimension
spirocyclic
architectures.
This
review
highlights
recent
advances,
emphasizes
mechanistic
discussions,
showcases
synthetic
applications
of
this
emerging
versatile
powerful
transformation.
The Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
88(7), P. 4854 - 4862
Published: March 22, 2023
A
metal/peroxide-free
involved
simple
cascade
6-exo-trig
spirocyclization
of
tert-butyl
nitrite
with
biaryl
ynones
has
been
finished,
which
resulted
in
various
NO2-modified
spiro[5,5]trienones
good
regioselectivity/yields.
variety
scaled-up
experiments,
reduction/epoxidation
operations,
and
mechanistic
studies
were
performed
to
verify
the
merits
process
this
radical
system.
Finally,
structure
spirocycles
was
confirmed
by
single-crystal
X-ray
diffraction.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(24), P. 4540 - 4545
Published: June 12, 2023
In
this
report
we
describe
an
atom-economic,
practical
strategy
for
the
synthesis
of
tri/tetra-substituted
furans
through
electrochemical
[3
+
2]
annulation
between
alkynes
and
β-keto
compounds
with
ferrocene
(Fc)
as
catalyst.
This
protocol
features
use
a
graphite
felt
(GF)
anode
stainless
steel
(SST)
cathode,
mild
conditions,
excellent
tolerance
various
compounds.
Additionally,
application
method
is
highlighted
by
late-stage
functionalization
complex
structures
gram-scale
experiment.
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.
Molecules,
Journal Year:
2025,
Volume and Issue:
30(5), P. 1143 - 1143
Published: March 3, 2025
Spirocalcaridines
A
and
B
are
among
the
most
challenging
members
of
marine
invertebrate-derived
Leucetta
alkaloids.
Approaches
to
construction
elaboration
highly
compact
spirocyclic
core
described.
The
synthesis
tricyclic
guanidine
via
tandem
oxidative
amination
dearomatizing
spirocyclization
(TOADS)
using
hypervalent
iodine
set
stage
for
total
migration
C4/C8
double
bond
C4/C5
position,
followed
by
oxidation.
undesired
but
not
surprising
propensity
cyclohexadienone
undergo
rearrangement
phenol
hindered
desired
olefin
migration.
Furthermore,
initial
efforts
install
oxidation
sequentially,
first
at
C5
then
C4
in
complete
carbon
skeleton,
were
fraught
with
unforeseen
challenges
unusual
outcomes.
In
addition,
scope
limitations
iodine-mediated
on
various
substrates
explored.
Urethanes
thiourethanes
underwent
an
excellent
yield,
whereas
reaction
allylic
species
lacking
p-methoxy
substituent
did
proceed.
Attempts
prepare
other
precursors
briefly
discussed.
