Organic Letters,
Год журнала:
2022,
Номер
24(20), С. 3668 - 3673
Опубликована: Май 17, 2022
An
effective
deoxygenative
C(sp3)-C(sp3)
bond
formation
reaction
is
achieved
through
electrochemical
reduction
of
alcoholic
phosphates
or
sulfonates
with
aldehydes
ketones.
Alcohol
derivatives
undergo
single-electron
under
conditions
followed
by
a
spontaneous
cleavage
the
C-O
exothermic
loss
phosphate
resulting
in
an
alkyl
radical
species.
Subsequently,
intermediates
are
further
reduced
to
carbanions
at
cathode,
which
situ
trapped
carbonyl
compounds,
thus
accomplishing
Barbier-type
reaction.
Chemical Reviews,
Год журнала:
2021,
Номер
122(2), С. 2487 - 2649
Опубликована: Ноя. 9, 2021
Redox
processes
are
at
the
heart
of
synthetic
methods
that
rely
on
either
electrochemistry
or
photoredox
catalysis,
but
how
do
and
catalysis
compare?
Both
approaches
provide
access
to
high
energy
intermediates
(e.g.,
radicals)
enable
bond
formations
not
constrained
by
rules
ionic
2
electron
(e)
mechanisms.
Instead,
they
1e
mechanisms
capable
bypassing
electronic
steric
limitations
protecting
group
requirements,
thus
enabling
chemists
disconnect
molecules
in
new
different
ways.
However,
while
providing
similar
intermediates,
differ
several
physical
chemistry
principles.
Understanding
those
differences
can
be
key
designing
transformations
forging
disconnections.
This
review
aims
highlight
these
similarities
between
comparing
their
underlying
principles
describing
impact
electrochemical
photochemical
methods.
European Journal of Organic Chemistry,
Год журнала:
2023,
Номер
26(21)
Опубликована: Апрель 7, 2023
Abstract
The
exceptional
versatility
of
carboxylic
acids
has
been
extensively
exploited
in
organic
synthesis
across
several
decades.
There
a
recent
upsurge
radical
decarboxylative
transformations.
process
can
be
initiated
under
mild
conditions,
and
the
resultant
radicals
have
orthogonal
reactivities
to
closed‐shell
species,
thus
providing
immense
opportunities
for
streamlining
novel
reactions.
use
free
is
most
desirable
owing
its
high
atom
step
economy.
Aiming
demonstrate
attractiveness
strategy
inspire
chemists
tackle
existing
challenges,
this
review
outlines
advances
on
functionalization
acids.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(42)
Опубликована: Сен. 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.
Advanced Synthesis & Catalysis,
Год журнала:
2021,
Номер
363(11), С. 2678 - 2722
Опубликована: Март 31, 2021
Abstract
Carboxylic
acids
are
among
the
most
used
feedstock
chemicals
due
to
their
great
structural
diversity
and
easy
handling.
The
use
of
carboxylic
derivatives
in
decarboxylative
couplings
has
proven
be
a
valuable
tool
for
construction
C−C
C‐heteroatom
bonds.
This
synthetic
strategy
provides
complementary
bond
disconnection
traditional
cross‐coupling
methods.
In
this
review,
we
provide
comprehensive
overview
decarboxylation‐initiated
intermolecular
formation,
outlining
several
main
mechanistic
concepts
combined
with
early
examples
highlighting
achievements
made
past
decade
until
January
2021.
these
reactions,
undergo
initial
decarboxylation
then
react
other
heteroatom
electrophiles
nucleophiles,
thus
replacing
carboxylate
group
prevalent
functionality.
magnified
image
Advanced Synthesis & Catalysis,
Год журнала:
2022,
Номер
364(24), С. 4189 - 4230
Опубликована: Дек. 3, 2022
Abstract
In
the
quest
for
sustainable
processes,
selection
of
resources
and
catalysts
is
central
importance.
Carboxylic
acids,
which
are
abundant,
stable
ideally
biobased
feedstocks,
can
be
considered
as
attractive
platforms
towards
a
range
functionalized
molecules.
A
recent
resurgence
photoinduced
ligand‐to‐metal
charge
transfer
(LMCT)
carboxylates
led
to
tremendous
developments
in
field
earth‐abundant
metal
mediated,
visible‐light
induced
(non)‐decarboxylative
transformations
carboxylic
acids.
These
reactions
combine
use
available
starting
materials,
low‐consuming
energy
source
abundant
catalysts.
Besides
these
undeniable
advantages,
they
also
provide
mild,
highly
selective
innovative
conditions
complex
molecule
functionalization.
The
objective
this
review
give
an
overview
advances
LMCT
with
special
focus
on
mechanistic
aspects
transformations.
magnified
image
ACS Catalysis,
Год журнала:
2022,
Номер
12(17), С. 10661 - 10667
Опубликована: Авг. 16, 2022
We
report
an
electrophotochemical
metal-catalyzed
strategy
that
harnesses
the
power
of
light
and
electricity
for
radical
decarboxylative
functionalization
aliphatic
carboxylic
acids.
This
environmentally
friendly
protocol
smoothly
converts
a
diverse
array
acids
into
corresponding
alkyl
azides
without
using
chemical
oxidants
or
azido-group
transfer
reagents.
The
visible
energy
electric
can
be
applied
in
spatially
separated
fashion
with
modular
electro-flow-cell
large-scale
synthesis.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(38)
Опубликована: Июль 31, 2023
Abstract
Decarboxylative
halogenation
reactions
of
alkyl
carboxylic
acids
are
highly
valuable
for
the
synthesis
structurally
diverse
halides.
However,
many
reported
protocols
rely
on
stoichiometric
strong
oxidants
or
electrophilic
halogenating
agents.
Herein,
we
describe
visible‐light
photoredox‐catalyzed
decarboxylative
N
‐hydroxyphthalimide‐activated
that
avoid
and
use
inexpensive
inorganic
halide
salts
as
Bromination
with
lithium
bromide
proceeds
under
simple,
transition‐metal‐free
conditions
using
an
organic
photoredox
catalyst
no
other
additives,
whereas
dual
photoredox‐copper
catalysis
is
required
chlorination
chloride.
The
mild
display
excellent
functional‐group
tolerance,
which
demonstrated
through
transformation
a
range
complex
acid
containing
natural
products
into
corresponding
bromides
chlorides.
In
addition,
show
generality
photoredox‐copper‐catalyzed
functionalization
by
extension
to
thiocyanation
potassium
thiocyanide,
was
applied
thiocyanates.
Chemistry - A European Journal,
Год журнала:
2022,
Номер
28(70)
Опубликована: Сен. 21, 2022
An
electrophotochemical
dual
metal-catalyzed
protocol
for
decarboxylative
arylation
of
simple
aliphatic
carboxylic
acids
with
aryl
halides
is
reported.
The
relative
stabilities
catalytically
active
metal
complexes
simultaneously
generated
at
anode
and
cathode
are
the
key
design
elements
success
this
convergent
paired
electrolysis.
This
new
electrophotocatalytic
method
mild,
robust,
most
importantly,
capable
accommodating
primary
including
acetic
acid
-
ubiquitous
variegated
structural
motifs
yet
remain
oddly
challenging
substrates
directly
as
native
functional
groups
C(sp2
)-C(sp3
)
bond
formation.
Chemical Communications,
Год журнала:
2022,
Номер
58(23), С. 3831 - 3834
Опубликована: Янв. 1, 2022
Here,
we
report
the
cerium-mediated
decarboxylative
alkylation
of
quinoxalin-2(1H)-ones
utilizing
feedstock
carboxylic
acids
as
a
radical
precursor
via
photoinduced-LMCT.
This
operationally
simple
protocol
overcomes
limitation
direct
use
to
access
alkyl
radicals.
Spectroscopic
investigations
reveal
photoinduced
LMCT
and
CO2
evolving
events.
We
have
utilized
broad
range
(1°
3°
acids),
amino
pharmaceutically-important
coupling
partner
synthesise
desired
alkylated
heterocyclic
product
in
good
excellent
yields.
