Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 15, 2025
ConspectusThe
homolytic
cleavage
of
C-C
bonds
adjacent
to
functional
groups
has
recently
become
a
popular
strategy
for
restructuring
the
skeletons
complex
organic
molecules.
In
contrast
traditional
reactivity
profiles
polar
bond
disconnections,
scission
furnishes
carbon-centered
free
radicals
primed
controlled
termination
with
diverse
range
radicophiles.
Beyond
standard
radical
capture,
transition-metal
catalysis
facilitates
sophisticated
and
C-heteroatom
bond-forming
reactions.
Intensive
efforts
have
been
focused
over
many
years
into
neighboring
carboxylic
acids
alcohols.
Despite
ubiquity
alkenes
ketones
in
natural
products,
feedstock
chemicals,
common
synthetic
intermediates,
much
less
attention
paid
exploiting
their
potential
diversifying
chiral
pool
materials,
such
as
terpenes
terpenoids.
Defunctionalization
this
manner
is
powerful
approach
synthesizing
high-value
chemicals
advanced
intermediates
because
possibility
reconstruct
further
decorate
chirality-bearing
carbon
skeletons.
Motivated
by
necessity,
since
2018
our
group
on
developing
ozonolysis-based
dealkenylative
molecular
diversification,
we
expanded
deacylation
2025.
Account,
chronicle
initial
motivation,
describe
historical
background,
summarize
research
deacylative
synthesis.
Our
capitalizes
ozonolysis
MeOH
generate
α-methoxyhydroperoxides
reaction
reducing
agents.
Their
reduction
through
single
electron
transfer,
mediated
transition
metal,
leads
formation
an
alkoxyl
that
undergoes
rapid
β-scission,
furnishing
both
ester
derived
from
acetal
atom.
The
produced
can
be
strategically
terminated
radicophiles,
thereby
delivering
remodeled
Using
concept,
developed
hydrodealkenylation
(through
hydrogen
atom
transfer
benzenethiol),
thiylation
thiyl
diaryl
disulfides),
alkenylation
addition/elimination
nitrostyrenes),
oxodealkenylation
treatment
TEMPO
followed
oxidation).
Furthermore,
kinetic
analysis
enabled
development
catalytic
FeII/vitamin
C
system
alkynylation
halodealkenylation.
Synergizing
copper
aminodealkenylation
net-redox-neutral
C-N
formation.
Although
high
oxidation
ozone
relative
compounds
makes
alkene-to-peroxide
conversion
possible,
it
also
limits
applicability
techniques
substrates
featuring
ozone-sensitive
groups.
We
overcame
constraint
first
applying
Isayama-Mukayiama
peroxidation
olefins
then
using
novel
system─catalytic
FeIII
PhSH
stoichiometric
γ-terpinene─for
ozone-free
hydrodealkenylation.
alkenes,
straightforward
methodology
well,
including
cycloalkanones.
This
process
applicable
total
syntheses
late-stage
modifications
ketone-containing
products.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(17)
Опубликована: Март 9, 2024
Abstract
The
molecular
structure‐editing
through
selective
C−C
bond
cleavage
allows
for
the
precise
modification
of
structures
and
opens
up
new
possibilities
in
chemical
synthesis.
By
strategically
cleaving
bonds
editing
structure,
more
efficient
versatile
pathways
synthesis
complex
compounds
could
be
designed,
which
brings
significant
implications
drug
development
materials
science.
o
‐Aminophenethyl
alcohols
amines
are
essential
key
motifs
bioactive
functional
material
molecules.
traditional
these
usually
requires
multiple
steps
generate
inseparable
isomers
induce
low
efficiencies.
leveraging
a
strategy,
we
herein
reported
ring‐opening
amination
isochromans
tetrahydroisoquinolines
‐aminophenethyl
amines.
This
innovative
chemistry
under
mild
transition
metal‐free
conditions.
Notably,
further
synthetic
application
demonstrated
that
our
method
provide
an
approach
to
components
diverse
Science,
Год журнала:
2025,
Номер
387(6738), С. 1108 - 1114
Опубликована: Март 6, 2025
The
synthesis
of
nitrogen-containing
molecules
through
carbon-nitrogen
(C-N)
bond
formation
is
critical
for
the
discovery
and
preparation
medicines,
agrochemicals,
materials.
Here,
we
report
direct
insertion
a
nitrogen
atom
into
unactivated
carbon-carbon
double
bonds
to
access
aza-allenium
intermediates,
which
can
be
converted
either
nitriles
or
amidine
products,
depending
on
initial
alkene
substitution
pattern.
This
operationally
simple
highly
functionally
compatible
reaction
works
wide
range
alkenes.
PIFA,
commercially
available
inexpensive
hypervalent
iodine
reagent,
key
this
reactivity.
Our
mechanistic
proposal
supported
by
chemical
trapping
experiments,
concomitantly
demonstrate
utility
our
method
valuable
N-heterocycles.
Additionally,
used
as
general
strategy
synthesizing
amides
amines,
well
15N-labeled
molecules.
The
synthesis
of
nitrogen-containing
molecules
through
C–N
bond
formation
is
critical
for
the
discovery
and
preparation
medicines,
agrochemicals
materials.
Traditional
synthetic
methods
using
alkenes
as
ubiquitous
substrates
leverage
reactivity
C(sp2)–C(sp2)
π
formation.
In
contrast,
that
can
form
bonds
complete
cleavage
double
are
scarce,
despite
considerable
potential
such
a
strategy.
Here,
we
report
direct
insertion
nitrogen
atom
into
unactivated
carbon-carbon
to
access
aza-allenium
intermediates
which
be
converted
either
nitriles
or
amidine
products,
depending
on
initial
alkene
substitution
pattern.
This
operationally
simple
highly
functional
group
tolerant
reaction
works
wide
range
alkenes.
Our
mechanistic
proposal
supported
by
chemical
trapping
experiments,
concomitantly
demonstrate
utility
our
method
valuable
N-heterocycles.
Overall,
this
study
demonstrates
possibility
reactive
(i.e.
aza-alleniums),
have
ample
downstream
diversification,
from
alkenes,
opening
new
avenues
important
products.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(58)
Опубликована: Авг. 8, 2024
Abstract
Mild
and
inexpensive
copper‐catalyzed
aromatization‐driven
ring‐opening
amination
oxygenation
of
spiro
dihydroquinazolinones
are
presented,
respectively.
These
protocols
provide
facile
atom‐economical
access
to
the
aminated
carbonyl‐containing
quinazolin‐4(3
H
)‐ones
in
good
yields
with
functional
group
compatibility,
which
difficult
obtain
by
conventional
methods.
Remarkably,
a
telescoped
procedure
involving
condensation
ring‐opening/functionalization
for
simple
cycloalkanone
was
found
be
accessible.
Mechanistic
studies
suggest
radical
pathway
this
transformation.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(17)
Опубликована: Март 9, 2024
Abstract
The
molecular
structure‐editing
through
selective
C−C
bond
cleavage
allows
for
the
precise
modification
of
structures
and
opens
up
new
possibilities
in
chemical
synthesis.
By
strategically
cleaving
bonds
editing
structure,
more
efficient
versatile
pathways
synthesis
complex
compounds
could
be
designed,
which
brings
significant
implications
drug
development
materials
science.
o
‐Aminophenethyl
alcohols
amines
are
essential
key
motifs
bioactive
functional
material
molecules.
traditional
these
usually
requires
multiple
steps
generate
inseparable
isomers
induce
low
efficiencies.
leveraging
a
strategy,
we
herein
reported
ring‐opening
amination
isochromans
tetrahydroisoquinolines
‐aminophenethyl
amines.
This
innovative
chemistry
under
mild
transition
metal‐free
conditions.
Notably,
further
synthetic
application
demonstrated
that
our
method
provide
an
approach
to
components
diverse
ACS Sustainable Chemistry & Engineering,
Год журнала:
2024,
Номер
12(34), С. 12719 - 12725
Опубликована: Авг. 15, 2024
Ozonolysis
is
a
highly
promising
reaction
for
biomass
valorization
due
to
high
efficiency,
value-added
carbonyl
products,
cheap
oxidant,
and
mild
conditions.
However,
the
generation
accumulation
of
explosive
peroxides
during
ozonolysis
can
be
risk
obstacle
large
application.
Herein,
we
propose
simple
method
that
treats
products
with
MnO2
decompose
reduce
complex
peroxides.
Here,
60–90%
removed
within
minutes
at
ambient
Solvent
substrate
structures
influence
activity.
We
further
novel
in
situ
MnO2-assisted
ozonolysis,
which
restrains
formation
while
promotes
aldehydes
formation.
Kinetic
investigations
indicated
H2O2
decomposition
low
concentration
first-order
reaction,
it
accelerated
an
involvement
second-order
organic
peroxide
generated
rapid
equilibrium
aldehyde.
This
work
suggests
enables
greener
more
sustainable
products.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 27, 2024
The
selective
reaction
of
cyclic
aminoperoxides
with
FeCl2
proceeds
through
a
sequence
O–O
and
C–C
bond
cleavages,
followed
by
intramolecular
cyclization,
yielding
functionalized
tetrahydrofurans
in
44–82%
yields.
Replacing
the
peroxyacetal
group
peroxide
structure
peroxyaminal
fragment
fundamentally
alters
pathway.
Instead
producing
linear
ketones,
this
modification
leads
to
formation
hard-to-access
substituted
tetrahydrofurans.
Although
aminoperoxide
cores
undergo
multiple
scissions,
cascade
is
atom-economical.
Computational
analysis
shows
that
O-ligands
at
Fe
center
have
enough
radical
character
promote
fragmentation
subsequent
cyclization.
stereoelectronic
flexibility
oxygen,
combined
iron's
capacity
stabilize
reactive
intermediates
during
multistep
cascade,
explains
efficiency
new
atom-economic
rearrangement.
Chemistry,
Год журнала:
2024,
Номер
6(5), С. 1246 - 1270
Опубликована: Окт. 15, 2024
Macrocycles
bridge
the
gap
between
conventional
small
molecules
and
polymers.
Drawing
inspiration
from
successful
carbon
heteroatom-containing
macrocycles,
peroxide-containing
macrocycles
are
gaining
attention
for
enhanced
bioactivity,
potential
chelating
properties,
applications
in
energetic
materials.
This
review
presents
following
strategies
construction
of
cyclic
peroxides
with
10-
to
36-membered
frameworks:
(1)
intramolecular
iodocyclization
hydroperoxides,
(2)
intermolecular
cyclization
hydroperoxides
alkyl
dihalides
or
carbonyls,
(3)
acid-catalyzed
rearrangements
ozonides
11-membered
triperoxides
via
oxy-
peroxycarbenium
ions,
(4)
peroxidation
carbonyls
targeting
macrocyclic
peroxides.
The
specific
agents
that
allow
selective
medium
large
cycles
also
analyzed.
