Advanced Synthesis & Catalysis,
Journal Year:
2024,
Volume and Issue:
366(21), P. 4274 - 4293
Published: Aug. 17, 2024
Abstract
Formates
are
abundantly
available
and
inexpensive
commodity
chemical,
widely
used
in
laboratory
industrial
organic
synthesis.
promising
hydrogen
carrier
green
C1
source,
have
also
been
a
subject
of
research
as
SET
reductants
recent
years.
Compared
to
the
toxic
flammable
gas
carbon
monoxide,
which
serves
formates
easier
handle,
store,
transport,
more
environmentally
friendly.
Therefore,
studies
radical
reactions,
formate
is
not
only
an
ideal
source
carbonyl,
great
significance
synthesize
carboxyl
compounds
with
various
structures,
but
reductant
for
editing
molecules
either
scientific
or
production.
The
activation
conversion
formate,
reductant,
very
challenging
hot
field
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(23)
Published: April 3, 2023
Carboxylation
of
easily
available
alkenes
with
CO2
is
highly
important
to
afford
value-added
carboxylic
acids.
Although
dicarboxylation
activated
alkenes,
especially
1,3-dienes,
has
been
widely
investigated,
the
challenging
unactivated
1,n-dienes
(n>3)
remains
unexplored.
Herein,
we
report
first
skipped
dienes
via
electrochemistry,
affording
valuable
dicarboxylic
Control
experiments
and
DFT
calculations
support
single
electron
transfer
(SET)
reduction
its
radical
anion,
which
followed
by
sluggish
addition
SET
unstabilized
alkyl
radicals
carbanions
nucleophilic
attack
on
give
desired
products.
This
reaction
features
mild
conditions,
broad
substrate
scope,
facile
derivations
products
promising
application
in
polymer
chemistry.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(24), P. 15991 - 16011
Published: Nov. 28, 2023
Carbon
dioxide
radical
anion
(CO2•–)
is
a
highly
reactive
nucleophilic
species
that
has
recently
emerged
in
organic
chemistry
as
strong
single
electron
donor
(reductant)
and
reactant
for
the
synthesis
of
carboxylic
acids.
In
general,
CO2•–
can
be
generated
by
either
direct
reduction
CO2
or
HAT
formate
salts.
Achievements
reactions
involving
have
been
witnessed
recent
years.
This
Review
summarizes
advances
highlighting
some
challenges
identifying
potential
areas
improvement,
which
may
offer
inspiration
future
studies.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(19), P. 13021 - 13033
Published: Sept. 21, 2023
Covalent
organic
frameworks
(COFs)
are
a
class
of
promising
porous
crystalline
materials
for
both
capturing
and
converting
CO2
into
high-value-added
products.
However,
long
synthesis
time
the
need
cocatalyst
restrict
its
potential
conversion.
Herein,
bipyridine-based
TAPT-BP-COF
with
high
crystallinity
as
skeleton
is
rapidly
synthesized
within
only
1
h
by
aid
supercritical
(scCO2)
activation.
Then,
production
dicationic
TAPT-BP2+-COF
accomplished
quaternization
reaction.
The
capture
capacity
improved
55.6%
due
to
CO2-philic
groups
(imine
triazine
groups),
polar
(−OH),
charged
skeleton,
suitable
pore
size,
thus
ensuring
sufficient
around
catalytic
active
sites.
Additionally,
outstanding
structure-enhanced
conversion
performance
observed
presence
synergistic
effect
between
–OH
Br–
in
skeleton.
rate-determining
step
cycloaddition
significantly
accelerated
without
any
solvents
cocatalysts
compared
individual
[OH-BP]2+[Br]2–
(BP2+
moiety).
Specifically,
efficiently
generates
cyclic
carbonate
heterogeneously
catalyzing
CO2-epoxide
yield
99.3%
has
excellent
stability
that
can
be
reused
ten
times
significant
activity
reduction.
This
work
provides
novel
perspective
targeted
design
rapid
COF-based
catalysts
efficiency
durability
Molecules,
Journal Year:
2023,
Volume and Issue:
28(16), P. 6127 - 6127
Published: Aug. 18, 2023
The
functionalisation
of
C–H
bonds
has
been
an
enormous
achievement
in
synthetic
methodology,
enabling
new
retrosynthetic
disconnections
and
affording
simple
equivalents
for
synthons.
Hydrogen
atom
transfer
(HAT)
is
a
key
method
forming
alkyl
radicals
from
substrates.
Classic
reactions,
including
the
Barton
nitrite
ester
reaction
Hofmann–Löffler–Freytag
reaction,
among
others,
provided
early
examples
HAT.
However,
recent
developments
photoredox
catalysis
electrochemistry
have
made
HAT
powerful
tool
capable
introducing
wide
range
functional
groups
into
bonds.
Moreover,
greater
mechanistic
insights
stimulated
development
increasingly
site-selective
protocols.
Site-selectivity
can
be
achieved
through
tuning
electron
density
at
certain
using
additives,
judicious
choice
reagent,
solvent
system.
Herein,
we
describe
latest
methods
functionalizing
C–H/Si–H/Ge–H
indirect
between
2018–2023,
as
well
critical
discussion
reagents,
aspects,
substrate
scopes,
background
contexts
Organic Chemistry Frontiers,
Journal Year:
2023,
Volume and Issue:
10(8), P. 2013 - 2017
Published: Jan. 1, 2023
A
synthetic
route
to
oxindole-3-acetic
acid
derivatives
is
disclosed
through
a
transition-metal
free
carbo-carboxylation
reaction
with
CO
2
˙
−
as
the
C1
source
in
situ
generated
from
formate
under
photo-induced
conditions.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(30), P. 16760 - 16770
Published: July 24, 2023
The
need
for
carbon-labeled
radiotracers
is
increasingly
higher
in
drug
discovery
and
development
(carbon-14,
β-,
t1/2
=
5730
years)
as
well
positron
emission
tomography
(PET)
vivo
molecular
imaging
applications
(carbon-11,
β+,
20.4
min).
However,
the
structural
diversity
of
still
systematically
driven
by
narrow
available
labeled
sources
methodologies.
In
this
context,
emergence
carbon
dioxide
radical
anion
chemistry
might
set
forth
potential
unexplored
opportunities.
Based
on
a
dynamic
isotopic
equilibration
between
formate
salts
[13C,
14C,
11C]CO2,
C-labeled
CO2•-
could
be
accessed
under
extremely
mild
conditions
within
seconds.
This
methodology
was
successfully
applied
to
hydrocarboxylation
dicarboxylation
reactions
late-stage
isotope
labeling
pharmaceutically
relevant
compounds.
relevance
method
radiochemistry
showcased
whole-body
PET
biodistribution
profile
[11C]oxaprozin
mice.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(4)
Published: Oct. 9, 2023
The
advancement
of
sustainable
photoredox
catalysis
in
synthetic
organic
chemistry
has
evolved
immensely
because
the
development
versatile
and
cost-effective
reagents.
In
recent
years,
a
substantial
effort
been
dedicated
to
exploring
utility
formic
acid
salts
various
photochemical
reactions.
this
context,
formates
have
demonstrated
diverse
capabilities,
functioning
as
reductants,
sources
carbonyl
groups,
reagents
for
hydrogen
atom
transfer.
Notably,
CO
