Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(16), P. 9326 - 9333
Published: April 13, 2023
We
report
that
the
dearomative
[4
+
2]
cycloaddition
between
1,2-dihydro-1,2,4,5-tetrazine-3,6-diones
(TETRADs)
and
benzenes,
naphthalenes,
or
N-heteroaromatic
compounds
under
visible
light
irradiation
affords
corresponding
isolable
cycloadducts.
Several
synthetic
transformations
including
transition-metal-catalyzed
allylic
substitution
reactions
using
isolated
cycloadducts
at
room
temperature
above
were
demonstrated.
Computational
studies
revealed
retro-cycloaddition
of
benzene–TETRAD
adduct
proceeds
via
an
asynchronous
concerted
mechanism,
while
benzene–MTAD
(MTAD
=
4-methyl-1,2,4-triazoline-3,5-dione)
a
synchronous
mechanism.
Science,
Journal Year:
2023,
Volume and Issue:
380(6640), P. 81 - 87
Published: April 6, 2023
The
Kolbe
reaction
forms
carbon-carbon
bonds
through
electrochemical
decarboxylative
coupling.
Despite
more
than
a
century
of
study,
the
has
seen
limited
applications
owing
to
extremely
poor
chemoselectivity
and
reliance
on
precious
metal
electrodes.
In
this
work,
we
present
simple
solution
long-standing
challenge:
Switching
potential
waveform
from
classical
direct
current
rapid
alternating
polarity
renders
various
functional
groups
compatible
enables
sustainable
carbon-based
electrodes
(amorphous
carbon).
This
breakthrough
enabled
access
valuable
molecules
that
range
useful
unnatural
amino
acids
promising
polymer
building
blocks
readily
available
carboxylic
acids,
including
biomass-derived
acids.
Preliminary
mechanistic
studies
implicate
role
in
modulating
local
pH
around
crucial
acetone
as
an
unconventional
solvent
for
reaction.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(15), P. 9307 - 9324
Published: July 18, 2022
Plastic
waste
triggers
a
series
of
concerns
because
its
disruptive
impact
on
the
environment
and
ecosystem.
From
point
view
catalysis,
however,
end-of-life
plastics
can
be
seen
as
an
untapped
feedstock
for
preparation
value-added
products.
Thus,
development
diversified
catalytic
approaches
valorization
is
urgent.
Previous
reviews
this
field
have
systematically
summarized
progress
made
plastic
reclamation.
In
review,
we
emphasize
design
processes
by
leveraging
state-of-the-art
technologies
from
other
developed
fields
to
derive
valuable
polymers,
functional
materials,
chemicals
plastics.
The
principles,
mechanisms,
opportunities
chemical
(thermo-,
electro-,
photocatalytic)
well
biocatalytic
ones
are
discussed,
which
may
provide
more
insights
future
processes.
Finally,
outlooks
perspectives
accelerate
toward
feasible
economy
discussed.
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: June 14, 2023
Photocatalytic
carboxylation
of
alkenes
with
CO2
is
a
promising
and
sustainable
strategy
to
synthesize
high
value-added
carboxylic
acids.
However,
it
challenging
rarely
investigated
for
unactivated
due
their
low
reactivities.
Herein,
we
report
visible-light
photoredox-catalyzed
arylcarboxylation
CO2,
delivering
variety
tetrahydronaphthalen-1-ylacetic
acids,
indan-1-ylacetic
indolin-3-ylacetic
chroman-4-ylacetic
acids
thiochroman-4-ylacetic
in
moderate-to-good
yields.
This
reaction
features
chemo-
regio-selectivities,
mild
conditions
(1
atm,
room
temperature),
broad
substrate
scope,
good
functional
group
compatibility,
easy
scalability
facile
derivatization
products.
Mechanistic
studies
indicate
that
situ
generation
carbon
dioxide
radical
anion
following
addition
might
be
involved
the
process.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(21)
Published: March 22, 2023
Birch
reduction
has
been
widely
used
in
organic
synthesis
for
over
half
a
century
as
powerful
method
to
dearomatize
arenes
into
1,4-cyclohexadiene
derivatives.
However,
the
conventional
reaction
using
liquid
ammonia
requires
laborious
procedures
ensure
inert
conditions
and
low
temperatures.
Although
several
ammonia-free
modifications
have
reported,
development
of
an
operationally
simple,
efficient,
scalable
protocol
remains
challenge.
Herein,
we
report
lithium-based
air
without
special
operating
ball-milling
technique.
This
is
characterized
by
its
operational
simplicity
extremely
short
time
(within
1
min),
probably
owing
situ
mechanical
activation
lithium
metal,
broad
substrate
scope,
no
requirement
dry
bulk
solvents.
The
potential
our
flash
also
demonstrated
efficient
bioactive
target
molecules
gram-scale
synthesis.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(42)
Published: Sept. 1, 2023
A
mild,
scalable
(kg)
metal-free
electrochemical
decarboxylation
of
alkyl
carboxylic
acids
to
olefins
is
disclosed.
Numerous
applications
are
presented
wherein
this
transformation
can
simplify
alkene
synthesis
and
provide
alternative
synthetic
access
valuable
from
simple
acid
feedstocks.
This
robust
method
relies
on
alternating
polarity
maintain
the
quality
electrode
surface
local
pH,
providing
a
deeper
understanding
Hofer-Moest
process
with
unprecedented
chemoselectivity.
Organic Process Research & Development,
Journal Year:
2024,
Volume and Issue:
28(2), P. 338 - 366
Published: Jan. 18, 2024
This
review
summarizes
examples
of
organic
electrosynthesis
from
the
peer-reviewed
literature
2000
to
2023
that
have
been
conducted
on
scales
20
g
or
above.
A
significant
portion
these
were
a
≤100
scale,
while
detailed
reports
kilogram-scale
remain
scarce
in
pharmaceutical
industry.
In
addition
chemical
transformation,
this
also
highlights
type
reactor
used
and
projected
productivity
metric
as
ways
compare
different
reports.
The
selected
scale-ups
described
herein
illustrate
remaining
challenges
currently
preventing
routine
use
large-scale
Chemical Science,
Journal Year:
2022,
Volume and Issue:
13(48), P. 14213 - 14225
Published: Jan. 1, 2022
This
Perspective
outlines
the
myriad
of
products
that
can
be
obtained
by
dearomatisation
and
functionalization
heteroarene
substrates.
Complex
3D
molecules
often
prepared
in
one
step
from
simple
arene
starting
materials.
