Synlett,
Journal Year:
2024,
Volume and Issue:
35(17), P. 1937 - 1946
Published: May 14, 2024
Abstract
The
cleavage
of
double
bonds
in
alkenes
constitutes
an
integral
process
converting
feedstock
materials
into
high-value
synthetic
intermediates.
Well-known
examples
such
as
the
oxidative
olefins
and
olefin
metathesis
only
facilitate
synthesis
oxygen-containing
compounds
recombination
olefins.
Therefore,
it
is
appealing
to
extend
C=C
bond
yield
more
abundant
transformations.
Herein,
we
report
a
novel
photocatalytic
approach
for
deconstructive
carboxylation
with
CO2
carboxylic
acids
absence
transition
metals.
Compared
reported
carboxylations
during
which
carbon
numbers
are
typically
increased,
achieve
exchange
dioxide
one
carbons
alkene
bond,
thus
providing
unchanged
when
terminal
used.
Chinese Journal of Chemistry,
Journal Year:
2024,
Volume and Issue:
42(18), P. 2249 - 2266
Published: May 15, 2024
Comprehensive
Summary
CO
2
is
an
abundant,
nontoxic,
and
renewable
C1
feedstock
in
synthetic
chemistry.
Direct
carboxylation
of
readily
available
olefins
incorporating
regarded
as
a
promising
strategy
to
access
high
value‐added
carboxylic
acids
well
fixation.
However,
due
the
thermodynamic
stability
kinetic
inertness
difficulty
controlling
regioselectivity,
with
still
remains
challenging.
Radical‐type
functionalization
represented
powerful
protocol
enabled
development
novel
transformations
this
realm.
More
recently,
advance
new
technology,
such
photoredox
catalysis
renaissance
electrochemistry
organic
synthesis,
offered
unique
chemical
reactivities
radical
precursors
provided
solutions
olefins.
This
review
presents
recent
advances
radical‐type
olefins,
which
has
mainly
been
achieved
through
photocatalysis
electrocatalysis
last
decade.
In
article,
we
provide
comprehensive
introduction
progress,
summarize
advantages
limitations
current
research,
discuss
potential
outlook
for
further
development.
Key
Scientists
Angewandte Chemie International Edition,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Jan. 31, 2025
Abstract
Cyclopropanes
are
valuable
motifs
in
organic
synthesis,
widely
featured
pharmaceuticals
and
functional
materials.
Herein,
we
report
an
efficient
electrochemical
methodology
for
the
cyclopropanation
of
alkenes,
leveraging
a
nickel‐catalyzed
process
continuous‐flow.
The
developed
protocol
demonstrates
broad
substrate
scope,
accommodating
both
electron‐rich
electron‐poor
alkenes
with
high
group
tolerance.
Beyond
dichloromethane
as
feedstock
methylene
source,
enables
synthesis
methylated,
deuterated,
chloro‐substituted
cyclopropanes.
Mechanistic
investigations
suggest
electro‐generation
nickel
carbene
key
intermediate.
Notably,
reaction
operates
under
ambient
conditions,
tolerates
air
moisture,
achieves
scalability
through
continuous‐flow
technology,
offering
straightforward
route
to
multi‐gram
quantities
enhanced
throughput.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(14), P. 3855 - 3860
Published: Jan. 1, 2024
The
CC
double
bond
cleavage
of
2-cyanoaryl
acrylamides
through
merging
2,3-butanedione
and
N
-hydroxysuccinimide
as
visible-light-enabled
hydrogen
atom
transfer
catalysts
is
effectively
established.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(31), P. 6664 - 6669
Published: July 30, 2024
A
photocatalytic
method
for
the
ring-closing
1,7-enyne
metathesis
using
α-amino
radical
as
an
alkene
deconstruction
auxiliary
is
present.
Preliminary
mechanistic
studies
suggest
that
intramolecular
1,5-hydrogen
atom
transfer
key
to
generation
and
β-scission
of
radical,
while
dearomatization
arenes
ring
opening
cyclopropanes
are
construct
spirocyclic
quinolin-2-ones.
This
approach
highlights
potential
metathesis,
providing
a
green,
efficient,
step-economical
way
synthesis
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(15), P. 4156 - 4167
Published: Jan. 1, 2024
An
in
situ
SO
2
F
-mediated
and
palladium-catalyzed
method
is
shown
for
the
decarboxylative
dehydrogenation
of
alkanecarboxylic
acids
cross-coupling
arenecarboxylic
acids,
respectively.
ACS Central Science,
Journal Year:
2024,
Volume and Issue:
11(1), P. 46 - 56
Published: Nov. 15, 2024
Herein,
we
report
a
visible-light-induced
charge-transfer-complex-enabled
dicarboxylation
and
deuterocarboxylation
of
C═C
bonds
with
oxalate
as
masked
CO2
source
under
catalyst-free
conditions.
In
this
reaction,
disclosed
the
first
example
that
tetrabutylammonium
could
be
able
to
aggregate
aryl
substrates
via
π–cation
interactions
form
charge
transfer
complexes,
which
subsequently
triggers
single
electron
from
oxalic
dianion
ammonium
countercation
irradiation
450
nm
bule
LEDs,
releasing
radical
anions.
Diverse
alkenes,
dienes,
trienes,
indoles,
including
challenging
trisubstituted
olefins,
underwent
anti-Markovnikov
high
selectivity
access
valuable
1,2-
1,4-dicarboxylic
acids
well
indoline-derived
diacids
β-deuterocarboxylic
mild
The
in
situ
generated
CO2•–
molecules
anions
both
add
bond
without
assistance
any
photocatalyst
or
additives,
made
reaction
sustainable,
clean,
efficient.
