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.
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.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(5), P. 2919 - 2927
Published: Jan. 26, 2024
Dicarboxylic
acids
and
derivatives
are
important
building
blocks
in
organic
synthesis,
biochemistry,
the
polymer
industry.
Although
catalytic
dicarboxylation
with
CO2
represents
a
straightforward
sustainable
route
to
dicarboxylic
acids,
it
is
still
highly
challenging
limited
generation
of
achiral
or
racemic
acids.
To
date,
asymmetric
give
chiral
has
not
been
reported.
Herein,
we
report
first
1,3-dienes
via
Cu
catalysis.
This
strategy
provides
an
efficient
environmentally
benign
high
regio-,
chemo-,
enantioselectivities.
The
copper
self-relay
catalysis,
that
is,
Cu-catalyzed
boracarboxylation
carboxylated
allyl
boronic
ester
intermediates
subsequent
carboxylation
C–B
bonds
dicarboxylates,
key
success
this
dicarboxylation.
Moreover,
protocol
exhibits
broad
substrate
scope,
good
functional
group
tolerance,
easy
product
derivatizations,
facile
synthesis
liquid
crystalline
polyester
drug-like
scaffolds.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(5), P. 2888 - 2894
Published: Jan. 26, 2024
Catalytic
asymmetric
carboxylation
of
readily
available
alkenes
with
CO2,
an
abundant
and
sustainable
one-carbon
building
block,
that
gives
access
to
value-added
α-stereogenic
carboxylic
acids
in
atom-
step-economic
manner
is
highly
attractive.
However,
it
has
remained
a
formidable
challenge
for
the
synthetic
community.
Here,
first
example
Cu-catalyzed
regio-
enantioselective
boracarboxylation
reaction
on
various
arylalkenes
diboron
under
atmospheric
pressure
CO2
described,
which
afforded
variety
chiral
β-boron-functionalized
α-aryl
up
87%
yield
97%
ee
mild
conditions.
Importantly,
α-substituted
could
also
be
subject
this
protocol
excellent
enantiopurities,
thereby
rendering
efficient
approach
generation
enantioenriched
α-chiral
all-carbon
quaternary
center.
Moreover,
high
functional
group
tolerance,
scalable
synthesis,
facile
bioactive
compounds,
like
(−)-scopolamine,
(−)-anisodamine,
(−)-tropicamide,
further
demonstrated
utility
strategy.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(4), P. 883 - 888
Published: Jan. 22, 2024
Herein,
we
present
a
transition-metal-free,
easy
handling
protocol
for
regioselective
carboxylation
of
gem-difluorostyrenes
with
sodium
formate
as
the
C1
source.
30
examples
α-fluoracrylates
were
obtained
in
yields
to
80%
under
these
conditions.
A
defluorinative
monofluorovinyl
intermediate
and
consecutive
photoinduced
electron
transfer
mechanism
proposed
after
investigation.
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
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(12), P. 9283 - 9293
Published: June 4, 2024
The
direct
reductive
functionalization
of
alkynes
under
mild
conditions
presents
a
promising
yet
challenging
avenue
for
accessing
value-added
molecules.
Alkyne
radical
anions
represent
distinct
class
reactive
intermediates
characterized
by
both
charge
and
an
unpaired
electron,
thus
holding
great
potential
facilitating
diverse
bond
formations,
particularly
in
alkyne
functionalization.
However,
the
synthetic
utility
is
limited,
primarily
due
to
difficulty
their
generation
formation
highly
unstable
vinyl
intermediates.
In
this
study,
we
accomplished
from
aryl
feedstocks
via
single
electron
transfer
(SET)
reduction
with
photogenerated
CO2
anion
(CO2•–),
enabling
hydroalkylation,
arylalkenylation,
hydrocarboxylation
alkynes.
Our
photocatalytic
strategy
features
metal-free
catalysis,
reaction
conditions,
employment
traceless
reductant,
good
functional
group
compatibility,
step-
atom-economy,
high
regioselectivity.
This
study
not
only
paves
way
leveraging
underexplored
but
also
catalyzes
ongoing
exploration
bifunctional
CO2•–
species
chemistry.
Precision Chemistry,
Journal Year:
2024,
Volume and Issue:
2(3), P. 88 - 95
Published: Feb. 16, 2024
γ-Butyrolactone
structures
are
commonly
found
in
various
natural
products
and
serve
as
crucial
building
blocks
organic
synthesis.
Consequently,
the
development
of
methods
for
synthesizing
γ-butyrolactones
has
garnered
significant
interest
within
synthesis
community.
In
this
study,
we
present
a
direct
highly
efficient
approach
from
allylic
alcohols.
Notably,
study
represents
first
instance
γ-butyrolactone
initiated
by
radical
hydrocarboxylation
using
CO2•–,
generated
metal
formates,
followed
cyclization.
This
two-step
process
is
achieved
through
synergistic
interaction
photoredox
hydrogen
atom
transfer
(HAT)
catalysis,
resulting
production
with
exceptional
efficiency.
Additionally,
when
employing
α,α-diaryl
alcohol
derivatives
substrates,
reaction
involves
1,2-aryl
migration,
which
occurs
concomitantly
CO2•–
addition,
leading
to
formation
4,5-substituted
lactones
good
yield.
The
artificial
force
induced
(AFIR)
method
identified
preferred
migration
pathway
along
potential
byproduct
pathways,
targeted
1,2-migration
was
be
most
plausible
pathway.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(14), P. 9750 - 9754
Published: June 28, 2024
Herein,
a
photocatalytic
umpolung
strategy
for
reductive
carboxylation
of
imines
the
synthesis
α-amino
acids
was
disclosed.
Carbon
dioxide
radical
anion
(CO
