Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(23)
Опубликована: Апрель 22, 2024
Abstract
The
construction
of
carbonyl
compounds
via
carbonylation
reactions
using
safe
CO
sources
remains
a
long‐standing
challenge
to
synthetic
chemists.
Herein,
we
propose
catalyst
cascade
Scheme
in
which
2
is
used
as
surrogate
the
benzyl
chlorides.
Our
approach
based
on
cooperation
between
two
coexisting
catalytic
cycles:
‐to‐CO
electroreduction
cycle
promoted
by
[Fe(TPP)Cl]
(TPP=meso‐tetraphenylporphyrin)
and
an
electrochemical
catalyzed
[Ni(bpy)Br
]
(2,2′‐bipyridine).
As
proof
concept,
this
protocol
allows
for
synthesis
symmetric
ketones
from
good
excellent
yields
undivided
cell
with
non‐sacrificial
electrodes.
reaction
can
be
directly
scaled
up
gram‐scale
operates
effectively
at
concentration
10
%,
demonstrating
its
robustness.
mechanistic
studies
cyclic
voltammetry,
IR
spectroelectrochemistry
Density
Functional
Theory
calculations
suggest
synergistic
effect
catalysts.
produced
reduction
key
formation
[Ni(bpy)(CO)
],
proposed
intermediate
responsible
C−C
bond
steps.
Chemical Reviews,
Год журнала:
2023,
Номер
123(19), С. 11269 - 11335
Опубликована: Сен. 26, 2023
Late-stage
functionalization
(LSF)
constitutes
a
powerful
strategy
for
the
assembly
or
diversification
of
novel
molecular
entities
with
improved
physicochemical
biological
activities.
LSF
can
thus
greatly
accelerate
development
medicinally
relevant
compounds,
crop
protecting
agents,
and
functional
materials.
Electrochemical
synthesis
has
emerged
as
an
environmentally
friendly
platform
transformation
organic
compounds.
Over
past
decade,
electrochemical
late-stage
(eLSF)
gained
major
momentum,
which
is
summarized
herein
up
to
February
2023.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(45)
Опубликована: Июнь 16, 2023
Abstract
Electrochemistry
utilizes
electrons
as
a
potent,
controllable,
and
traceless
alternative
to
chemical
oxidants
or
reductants,
typically
offers
more
sustainable
option
for
achieving
selective
organic
synthesis.
Recently,
the
merger
of
electrochemistry
with
readily
available
electrophiles
has
been
recognized
viable
increasingly
popular
methodology
efficiently
constructing
challenging
C−C
C‐heteroatom
bonds
in
manner
complex
molecules.
In
this
mini‐review,
we
have
systematically
summarized
most
recent
advances
electroreductive
cross‐electrophile
coupling
(eXEC)
reactions
during
last
decade.
Our
focus
on
electrophiles,
including
aryl
alkyl
(pseudo)halides,
well
small
molecules
such
CO
2
,
SO
D
O.
Green Chemistry,
Год журнала:
2023,
Номер
25(17), С. 6538 - 6560
Опубликована: Янв. 1, 2023
An
activation
toolbox
for
the
effective
catalytic
conversion
of
CO
2
to
chemicals
is
proposed
along
with
challenges
and
prospects
related
future
development
this
exciting
technology.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(23)
Опубликована: Апрель 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,
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:
2023,
Номер
145(20), С. 10967 - 10973
Опубликована: Апрель 19, 2023
Despite
the
widespread
applications
of
α-hydroxyalkyl
cyclic
amines,
direct
and
diverse
access
to
such
a
class
unique
vicinal
amino
alcohols
still
remains,
date,
challenge.
Here,
through
strategy
electroreductive
α-hydroxyalkylation
inactive
N-heteroarenes
with
ketones
or
electron-rich
arylaldehydes,
we
describe
room
temperature
approach
for
construction
which
features
broad
substrate
scope,
operational
simplicity,
high
chemoselectivity,
no
need
pressurized
H2
gas
transition
metal
catalysts.
The
zinc
ion
generated
from
anode
oxidation
plays
crucial
role
in
activation
both
reactants
by
decreasing
their
reduction
potentials.
electroreduction
combination
Lewis
acids
this
work
is
anticipated
develop
more
useful
transformations.
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.
