ACS Catalysis,
Год журнала:
2023,
Номер
13(24), С. 15991 - 16011
Опубликована: Ноя. 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,
Год журнала:
2024,
Номер
146(5), С. 2888 - 2894
Опубликована: Янв. 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.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Март 30, 2024
Abstract
Herein,
we
report
an
electroreduction
of
unactivated
alkyl
alkenes
enabled
by
[Fe]-H,
which
is
provided
through
the
combination
anodic
iron
salts
and
silane
generated
in
situ
via
cathodic
reduction,
using
H
2
O
as
H-source.
The
catalytic
amounts
Si-additive
work
H-carrier
from
to
generate
a
highly
active
species
under
continuous
electrochemical
conditions.
This
approach
shows
broad
substrate
scope
good
functional
group
compatibility.
In
addition
hydrogenation,
use
D
instead
provides
desired
deuterated
products
yields
with
excellent
D-incorporation
(up
>99%).
Further
late-stage
hydrogenation
complex
molecules
drug
derivatives
demonstrate
potential
application
pharmaceutical
industry.
Mechanistic
studies
are
performed
provide
support
for
proposed
mechanistic
pathway.
Chinese Journal of Chemistry,
Год журнала:
2024,
Номер
42(18), С. 2249 - 2266
Опубликована: Май 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
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(21), С. 14864 - 14874
Опубликована: Май 16, 2024
The
exploitation
of
carbon
dioxide
(CO2)
as
a
sustainable,
plentiful,
and
harmless
C1
source
for
the
catalytic
synthesis
enantioenriched
carboxylic
acids
has
long
been
acknowledged
pivotal
task
in
synthetic
chemistry.
Herein,
we
present
current-driven
nickel-catalyzed
reductive
carboxylation
reaction
with
CO2
fixation,
facilitating
formation
C(sp3)–C(sp2)
bonds
by
circumventing
handling
moisture-sensitive
organometallic
reagents.
This
electroreductive
protocol
serves
practical
platform,
paving
way
propargylic
(up
to
98%
enantiomeric
excess)
from
racemic
carbonates
CO2.
efficacy
this
transformation
is
exemplified
its
successful
utilization
asymmetric
total
(S)-arundic
acid,
(R)-PIA,
(S)-chizhine
D,
(S)-cochlearin
G,
(S,S)-alexidine,
thereby
underscoring
potential
electrosynthesis
achieve
complex
molecular
architectures
sustainably.
Chemical Science,
Год журнала:
2024,
Номер
15(16), С. 6178 - 6183
Опубликована: Янв. 1, 2024
Low-cost
formate
salt
was
used
as
the
reductant
and
part
of
carboxyl
source
in
a
visible-light-driven
dicarboxylation
diverse
alkenes,
including
simple
styrenes.
The
highly
competing
hydrocarboxylation
side
reaction
successfully
overridden.
Good
yields
products
were
obtained
under
mild
conditions
at
ambient
temperature
pressure
CO
ACS Catalysis,
Год журнала:
2024,
Номер
14(12), С. 9283 - 9293
Опубликована: Июнь 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.
