Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Oct. 31, 2024
Abstract
We
report
herein
our
studies
on
the
direct
photoactivation
of
carbonyl
cyclopropanes
to
give
biradical
intermediates,
leading
selective
cleavage
more
substituted
carbon‐carbon
bond.
Depending
substrate
structure,
extended
alkenes
were
isolated
or
directly
reacted
in
a
photo‐Nazarov
process
bicyclic
products.
Based
these
results,
unified
reductive
ring‐opening
reaction
was
developed
by
using
diphenyl
disulfide
as
hydrogen
atom
transfer
(HAT)
reagent.
By
performing
sequential
cyclopropanation/selective
ring
opening
reaction,
we
achieved
CH
2
insertion
into
α,β
bond
both
acyclic
and
cyclic
unsaturated
compounds.
Our
protocol
provides
further
tool
for
modification
carbon
framework
organic
compounds,
complementing
recent
progress
“skeletal
editing”.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(48)
Published: Oct. 11, 2023
Abstract
N
‐Heterocyclic
carbene
(NHC)
catalyzed
radical‐radical
reactions
have
been
proven
to
be
powerful
strategies
for
assembling
ketyl‐containing
compounds
via
single
electron
transfer
(SET)
pathway
under
either
thermal
conditions
or
photoredox
conditions.
In
this
context,
acylation
of
alkenes
radical
relay
NHC‐organocatalysis
has
also
opened
a
new
window
the
difunctionalization
construct
valuable
molecules
in
organic
synthesis.
review,
advances
and
progress
were
summarized
according
different
ways
generation
key
NHC‐bound
ketyl‐type
radicals.
Furthermore,
reaction
scopes,
limitations
mechanisms
discussed
based
on
types
catalytic
systems.
Conclusions
perspectives
put
forward
at
end.
Chemistry - A European Journal,
Journal Year:
2024,
Volume and Issue:
30(47)
Published: Aug. 2, 2024
Abstract
Developing
methods
to
directly
transform
C(sp
3
)
−H
bonds
is
crucial
in
synthetic
chemistry
due
their
prevalence
various
organic
compounds.
While
conventional
protocols
have
largely
relied
on
transition
metal
catalysis,
recent
advancements
organocatalysis,
particularly
with
radical
NHC
catalysis
sparked
interest
the
direct
functionalization
of
“inert”
for
cross
C−C
coupling
carbonyl
moieties.
This
strategy
involves
selective
cleavage
generate
key
carbon
radicals,
often
achieved
via
hydrogen
atom
transfer
(HAT)
processes.
By
leveraging
bond
dissociation
energy
(BDE)
and
polarity
effects,
HAT
enables
rapid
diverse
)−H
substrates,
such
as
ethers,
amines,
alkanes.
mini‐review
summarizes
progress
carbene
organocatalytic
inert
enabled
by
processes,
categorizing
them
into
two
sections:
1)
C−H
involving
acyl
azolium
intermediates;
2)
reductive
Breslow
intermediates.
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 Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(11), P. 3089 - 3099
Published: Jan. 1, 2024
NHC
and
photocatalysis
dual-catalyzed
mono/difluoromethylative
acylation
of
1,3-enynes
was
realized,
providing
fluormethyl-substituted
allenyl
ketones.
SO
2
might
play
a
critical
role
in
achieving
high
reactivity
selectivity.
JACS Au,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 28, 2025
The
C–N
bonded
aromatic
compounds
have
demonstrated
potential
applications
in
energetic
materials,
polymers,
agrochemicals,
and
medicinal
chemistry.
Developing
improved
methodologies
for
the
streamlined
economical
generation
of
bonds
is
highly
sought-after.
In
this
study,
an
efficient
strategy
was
developed
to
construct
bis-heterocyclic
compounds.
A
total
26
substrates
with
different
functional
groups
substituted
azoles
were
selected
react
1,3,4-trinitropyrazole.
results
demonstrate
that
coupling
reaction
predominantly
influenced
by
pKa
substrates.
relationships
between
products
meticulously
investigated
determined.
Among
those
products,
3a–3d
exhibit
high
thermostability
comparable
detonation
properties
RDX,
indicating
significant
use
as
secondary
explosives.
method
presented
work
may
also
serve
a
powerful
toolkit
design
synthesize
domains
chemistry
organic
materials.
The Chemical Record,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 26, 2025
Abstract
Transforming
alkane
C−H
bonds
into
carbon‐carbon
and
carbon‐heteroatom
represents
a
paramount
objective
in
synthetic
chemistry
with
significant
implications
for
sustainable
production.
Although
transition‐metal
catalysts
such
as
Pd,
Rh
etc
have
dominated
this
field,
recent
breakthroughs
metal‐free
approaches
leveraging
small‐molecule
or
photogenerated
intermediates
emerged
efficient
alternatives.
These
facilitate
precise
bond
activation
selective
formation
of
C−X
(e.
g.,
C,
halogen,
N,
O)
under
mild
conditions,
thereby
paving
promising
avenue
eco‐friendly
transformations.
This
review
provides
an
overview
advancements
homogeneous
functionalization,
focusing
on
organocatalytic
photoinduced
strategies,
the
aim
enhancing
mechanistic
understanding
inspiring
development
innovative
methodologies
conversion
alkanes
high‐value
compounds.
Nature Communications,
Journal Year:
2025,
Volume and Issue:
16(1)
Published: April 7, 2025
Abstract
Enantioenriched
α
-chiral
β
-fluorinated
ketones
are
valuable
structural
motifs
with
application
in
several
fields.
The
recently
emerged
concept
of
NHC-catalyzed
radical
acyl-trifluoromethylation
olefins
offers
a
rapid
route
to
construct
racemic
single
step.
Due
the
lack
competent
chiral
NHC
catalysts
constructing
these
molecules
an
enantioselective
manner
remains
unmet
challenge.
Herein,
we
report
family
thiazolium
carbenes
having
bulky
flanking
groups
and
offering
three
distinct
positions
broad
steric
electronic
tunability.
display
so
far
unmatched
enantioselectivities
for
acyl-trifluoromethylations
simple
unactivated
wide
variety
aldehydes
Togni’s
reagent.
method
provides
enantioenriched
-trifluoromethylated
high
yields
excellent
up
98:2
er.
A
potential
applicability
this
methodology
is
demonstrated
through
enantio-
diastereoselective
late-stage
functionalizations
pharmaceutical
compounds.
