Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(12), С. 8425 - 8434
Опубликована: Март 15, 2024
The
precise
design
of
catalytic
metal
centers
with
multiple
chemical
states
to
facilitate
sophisticated
reactions
involving
multimolecular
activation
is
highly
desirable
but
challenging.
Herein,
we
report
an
ordered
macroporous
catalyst
heterovalent
pair
(HMP)
sites
comprising
CuII–CuI
on
the
basis
a
microporous
metal–organic
framework
(MOF)
system.
This
HMP
proximity
dual
copper
sites,
whose
distance
controlled
∼2.6
Å,
macropore
surface
exhibits
co-activation
behavior
ethanol
at
CuII
and
alkyne
CuI,
avoids
restriction,
thereby
promoting
additive-free
hydroboration
reaction.
desired
yield
enhances
dramatically
compared
pristine
MOF
both
solely
isovalent
CuII–CuII
sites.
Density
functional
theory
calculations
reveal
that
Cu-HMP
can
stabilize
Bpin-CuII–CuI-alkyne
intermediate
C–B
bond
formation,
resulting
in
smooth
process.
work
provides
new
perspectives
catalysts
for
matter
transformations.
Chemical Communications,
Год журнала:
2024,
Номер
60(50), С. 6340 - 6361
Опубликована: Янв. 1, 2024
In
this
review,
the
state-of-the-art
advances
in
radical-involved
C(sp
3
)–N
bond
formation
via
metallaphotoredox
catalysis
have
been
highlighted,
which
are
organized
according
to
different
catalytic
modes,
reaction
types,
and
substrate
classes.
Ketones
are
ubiquitous
in
bioactive
natural
products,
pharmaceuticals,
chemical
feedstocks,
and
synthetic
intermediates.
Hence,
deacylative
coupling
reactions
enable
the
versatile
elaboration
of
a
plethora
chemicals
to
access
complex
drug
candidates
products.
Here,
we
present
arylation
alkynylation
strategies
for
synthesis
wide
range
alkyl-tethered
arenes
alkynes
from
cyclic
ketones
methyl
under
dual
nickel/photoredox
catalysis.
This
reaction
begins
by
generating
pre-aromatic
intermediate
(PAI)
through
condensation
ketone
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 7, 2025
The
homolytic
cleavage
of
C–C
bonds
adjacent
to
specific
functional
groups
has
lately
emerged
as
a
versatile
approach
for
molecular
diversification.
Despite
the
ubiquity
and
synthetic
utility
ketones,
radical
fragmentation
their
α-C–C
proven
be
formidable
challenge.
Here,
we
present
broadly
applicable
deacylative
strategy
designed
homolytically
cleave
aliphatic
ketones
various
complexities,
including
transformations
cycloalkanones
into
carboxylic
acids
tethered
C-centered
free
radicals
that
can
engaged
in
diverse
radical-based
processes.
method
involves
ketone
activation
through
treatment
with
hydrogen
peroxide,
yielding
gem-dihydroperoxides.
Subsequent
single-electron-transfer
reduction
mediated
by
low-valent
metal
complex
generates
alkyl
captured
selectively
radicophile
choice,
catalytic
cross-coupling.
logic
our
functionalization
is
exemplified
total
synthesis
14
natural
products,
one
analogue,
two
drugs
starting
from
readily
available
showcasing
its
transformative
power
settings.
This
obviates
need
reagents
allows
controlled
conversion
reconstructed
making
process
highly
across
spectrum
domains.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 15, 2025
Advancements
in
radical
capture
strategies
have
expanded
the
range
of
products
accessible
from
alkenes
through
dealkenylative
synthesis.
These
methods,
however,
are
still
limited,
as
they
rely
on
ozonolysis
to
generate
key
peroxide
intermediates
alkenes.
Ozonolysis
has
several
limitations.
It
is
not
compatible
with
containing
electron-rich
aromatics.
also
inapplicable
certain
alkene
substitution
patterns
context
Additionally,
it
struggles
sterically
hindered
alkenes,
internal
nucleophiles
and
electrophiles,
allylic
alcohols.
In
this
paper,
using
Isayama-Mukaiyama
peroxidation
(IMP),
we
address
limitations
rescue
previously
inaccessible
substrates
broaden
applicability
functionalization.
particular,
apply
IMP
hydrodealkenylation
describe
a
novel
hydrogenation
condition─employing
catalytic
[FeIII],
benzenethiol,
γ-terpinene
refluxing
methanol─to
resolve
β-scission
issues
associated
IMP-generated
alkyl
silylperoxides.
Advanced Synthesis & Catalysis,
Год журнала:
2024,
Номер
366(7), С. 1595 - 1605
Опубликована: Фев. 3, 2024
Abstract
Herein,
we
present
a
photoinduced
deconstructive
alkoxyamination
of
alkyl
alcohols
catalyzed
by
iron
salts.
This
transformation
involves
the
initiation
alkoxy
radicals
through
chlorine
radical‐induced
radical
formation,
followed
β
‐scission
and
trapping
resulting
carbon
with
2,2,6,6‐tetramethylpiperidin‐1‐yl
(TEMPO).
reaction
exhibits
broad
substrate
scope
(40
examples),
including
primary
secondary
that
are
prone
to
oxidation
combination
TEMPO
iron.
Mechanistic
investigations
have
revealed
enhanced
coordination
chloride
ion
center
inhibits
OH
process,
thereby
enabling
tolerance
alcohols.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Июль 17, 2024
Abstract
Molecular
structure-editing
through
nitrogen
insertion
offers
more
efficient
and
ingenious
pathways
for
the
synthesis
of
nitrogen-containing
compounds,
which
could
benefit
development
synthetic
chemistry,
pharmaceutical
research,
materials
science.
Substituted
amines,
especially
alkyl
heterocyclic
are
widely
found
in
nature
products
drugs.
Generally,
accessing
these
compounds
requires
multiple
steps,
result
low
efficiency.
In
this
work,
a
molecular
editing
strategy
is
used
to
realize
using
aryl
alkanes
as
starting
materials.
Using
derivatives
O
-tosylhydroxylamine
source,
method
enables
precise
into
C
sp
2
-C
3
bond
alkanes.
Notably,
further
applications
demonstrate
that
be
prepare
bioactive
molecules
with
good
efficiency
modify
skeleton
Furthermore,
plausible
reaction
mechanism
involving
transformation
carbocation
imine
intermediates
has
been
proposed
based
on
results
control
experiments.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
89(8), С. 5699 - 5714
Опубликована: Апрель 2, 2024
Four
heteroatoms
dance
in
the
cascade
of
four
pericyclic
reactions
initiated
by
ozonolysis
C═N
bonds.
Switching
from
imines
to
semicarbazones
introduces
fifth
heteroatom
that
slows
this
dance,
delays
reaching
thermodynamically
favorable
escape
path,
and
allows
efficient
interception
carbonyl
oxides
(Criegee
intermediates,
CIs)
an
external
nucleophile.
The
new
three-component
reaction
alcohols,
ozone,
oximes/semicarbazones
greatly
facilitates
synthetic
access
monoperoxyacetals
(alkoxyhydroperoxides).
Accounts of Chemical Research,
Год журнала:
2025,
Номер
unknown
Опубликована: Фев. 27, 2025
ConspectusStable
and
inert
C-C
bonds
form
the
fundamental
framework
of
organic
compounds.
Consequently,
direct
transformations
involving
bond
cleavage
present
an
innovative
approach
for
rapid
modification
remodeling
molecular
skeletons.
In
recent
years,
concept
skeletal
editing
has
garnered
widespread
attention
been
significantly
developed,
providing
new
opportunities
late-stage
bioactive
molecules,
high-value
transformation
bulk
chemicals,
a
revolution
in
traditional
fragment
coupling
strategies
chemical
synthesis.
Notable
advancements
this
field
have
focused
on
cyclic
including
ring
expansion,
contraction,
ring-opening
reactions,
thereby
enriching
synthetic
toolbox
available
to
chemists.
However,
selective
remains
formidable
challenge,
especially
complex
due
high
dissociation
energy
difficulty
achieving
precise
selectivity
control.
Over
past
few
our
group
made
efforts
address
these
challenges.
We
demonstrated
potential
molecule
reactions
as
efficient
strategy
synthesis
molecules.Herein,
we
two
major
thematic
achieved
by
group,
utilizing
cascade
activation
entropy-driven
reconstruction
via
cleavage.
These
are
characterized
mild
conditions,
accessibility
catalysts
reagents,
exceptional
functional
compatibility,
emerging
novel
approaches
through
atom-incorporation
mainly
nitrogenation,
oxygenation,
halogenation
synthesize
pharmaceuticals,
natural
products,
material
molecules.
(1)
Ring
expansion
reactions:
developed
that
enable
insertion
C-,
N-,
O-containing
units
into
rings.
methodologies
offer
practical
routes
synthesizing
amides,
amines,
lactones,
nitrogen-containing
heterocycles.
(2)
Ring-opening
enables
construction
distally
difunctionalized
frameworks.
By
transition
metal
catalysis
radical-mediated
process,
successfully
both
single
C═C
double
within
Furthermore,
tackled
highly
challenging
arene
(ARO)
reaction,
enabling
stereoselective
conjugated
systems
unsaturation
liberation
aromatic
systems.
Mechanistic
studies
DFT
calculations
provided
critical
insights
processes.
also
identified
key
intermediates
involved
cleavage,
benzyl
azide,
O-acetyl
hydroxylamine,
β-azido
peroxyl
radical,
copper
bisnitrene,
2-nitrene
indazole.
findings
deepened
understanding
mechanisms
strategy,
which
further
promoted
discovery
related
acyclic
substrates.
Science,
Год журнала:
2025,
Номер
387(6738), С. 1083 - 1090
Опубликована: Март 6, 2025
Deconstructive
transformation
of
carbon-carbon
double
bonds
(C=C)
is
a
pivotal
strategy
in
synthetic
chemistry
and
drug
discovery.
Despite
the
substantial
advances
olefin
metathesis
ozonolysis
for
natural
product
synthesis
through
C=C
double-bond
cleavage,
catalytic
remodeling
complex
molecules
deconstruction
has
been
underdeveloped.
We
report
heterogeneous
copper-catalyzed
which
enables
by
converting
carbons
on
either
side
bond
to
carbonyl
cyano
groups,
respectively.
In
particular,
this
method
provides
an
efficient
protocol
conveniently
transform
terpenoids,
glycals,
steroids,
bioactive
privileged
scaffolds
with
underexplored
chemical
space.
