Beilstein Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
20, P. 2500 - 2566
Published: Oct. 9, 2024
With
the
resurgence
of
electrosynthesis
in
organic
chemistry,
there
is
a
significant
increase
number
routes
available
for
late-stage
functionalization
(LSF)
drugs.
Electrosynthetic
methods,
which
obviate
need
hazardous
chemical
oxidants
or
reductants,
offer
unprecedented
control
reactions
through
continuous
variation
applied
potential
and
possibility
combination
with
photochemical
processes.
This
capability
substantial
advantage
performing
electrochemical
photoelectrochemical
LSF.
Ultimately,
these
protocols
are
poised
to
become
vital
component
medicinal
chemist's
toolkit.
In
this
review,
we
discuss
that
have
been
demonstrated
be
applicable
LSF
pharmaceutical
drugs,
their
derivatives,
natural
substrates.
We
present
analyze
representative
examples
illustrate
electrochemistry
photoelectrochemistry
valuable
molecular
scaffolds.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(16), P. 6513 - 6519
Published: Feb. 4, 2020
The
first
electrochemical
approach
for
nickel-catalyzed
cross-electrophile
coupling
was
developed.
This
method
provides
a
novel
route
to
1,1-diarylalkane
derivatives
from
simple
and
readily
available
alkyl
aryl
halides
in
good
yields
excellent
regioselectivity
under
mild
conditions.
procedure
shows
tolerance
broad
variety
of
functional
groups
both
primary
secondary
can
be
used.
Furthermore,
the
reaction
successfully
scaled
up
multigram
scale,
thus
indicating
potential
industrial
application.
Mechanistic
investigation
suggested
formation
nickel
hydride
electroreductive
chain-walking
arylation,
which
led
development
new
hydroarylation
styrenes
provide
series
1,1-diaryl
alkanes
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(19), P. 11269 - 11335
Published: Sept. 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.
Chemical Reviews,
Journal Year:
2024,
Volume and Issue:
124(9), P. 6078 - 6144
Published: April 17, 2024
Alcohols
are
abundant
and
attractive
feedstock
molecules
for
organic
synthesis.
Many
methods
their
functionalization
require
them
to
first
be
converted
into
a
more
activated
derivative,
while
recent
years
have
seen
vast
increase
in
the
number
of
complexity-building
transformations
that
directly
harness
unprotected
alcohols.
This
Review
discusses
how
transition
metal
catalysis
can
used
toward
this
goal.
These
broadly
classified
three
categories.
Deoxygenative
functionalizations,
representing
derivatization
C–O
bond,
enable
alcohol
act
as
leaving
group
formation
new
C–C
bonds.
Etherifications,
characterized
by
O–H
represent
classical
reactivity
has
been
modernized
include
mild
reaction
conditions,
diverse
partners,
high
selectivities.
Lastly,
chain
reactions
described,
wherein
acts
mediator
formal
C–H
alkyl
backbone.
Each
these
classes
transformation
will
discussed
context
intermolecular
arylation,
alkylation,
related
reactions,
illustrating
alcohols
harnessed
Chemical Society Reviews,
Journal Year:
2024,
Volume and Issue:
53(9), P. 4607 - 4647
Published: Jan. 1, 2024
This
review
collectively
discussed
the
utilisation
of
alcohols
in
various
organic
transformations
and
their
application
toward
intermediates
drugs,
drug
derivatives
natural
product-like
molecules.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(31), P. 12842 - 12847
Published: April 24, 2020
Abstract
The
chemical
use
of
CO
2
as
an
inexpensive,
nontoxic
C1
synthon
is
utmost
topical
interest
in
the
context
carbon
capture
and
utilization
(CCU).
We
present
merger
cobalt
catalysis
electrochemical
synthesis
for
mild
catalytic
carboxylations
allylic
chlorides
with
.
Styrylacetic
acid
derivatives
were
obtained
moderate
to
good
yields
functional
group
tolerance.
thus‐obtained
products
are
useful
versatile
synthons
γ‐arylbutyrolactones.
Cyclic
voltammetry
operando
kinetic
analysis
performed
provide
mechanistic
insights
into
electrocatalytic
carboxylation
Chemistry - A European Journal,
Journal Year:
2021,
Volume and Issue:
27(49), P. 12453 - 12508
Published: May 26, 2021
Synthetic
organic
chemistry
has
witnessed
a
plethora
of
functionalization
and
defunctionalization
strategies.
In
this
regard,
C-H
been
at
the
forefront
due
to
multifarious
applications
in
development
simple
complex
molecular
architectures
holds
brilliant
prospect
drug
discovery.
Despite
explored
tremendously
by
chemists,
strategy
still
enjoys
employment
novel
metal
catalysts
as
well
metal-free
ligands.
Moreover,
switch
photo-
electrochemistry
widened
our
understanding
alternative
pathways
via
which
reaction
can
proceed
these
strategies
have
garnered
prominence
when
applied
activation.
chemists
foraging
for
new
directing
groups
templates
selective
activation
bonds
from
myriad
carbon-hydrogen
aromatic
aliphatic
systems.
As
matter
fact,
varying
groups,
scientists
found
answer
challenge
distal
bond
remained
an
obstacle
very
long
time.
These
frequently
harnessed
selectively
activating
natural
products,
drugs,
macromolecules
decorated
with
multiple
bonds.
This
itself
was
before
commencement
field
site
other
than
targeted
could
modify
hamper
biological
activity
pharmacophore.
Total
synthesis
pharmacophore
often
faces
difficulty
superfluous
steps
towards
functionalization.
solved
late-stage
simply
harnessing
green
conditions
seen
light
past
few
decades
rising
concern
about
environmental
issues.
Therefore,
or
usage
non-toxic
metals
recently
showcased
number
elegant
works.
Also,
research
across
world
are
developing
rational
group
free
non-directed
protocols
that
just
guided
review
encapsulates
works
pertinent
discusses
science
devoted
it
fundamental
level.
gives
readers
broad
how
work,
execution
various
catalysts,
groups.
not
only
helps
budding
scientist
his/her
but
also
matured
mind
searching
out
A
detailed
picture
its
progress
time
portrayed
lucid
scientific
language
motive
inculcate
educate
minds
beautiful
overview
most
relevant
significant
era.
The
unique
trait
is
description
classification
their
utility
over
wide
substrate
scope.
allows
experimental
chemist
understand
applicability
domain
employ
any
substrate.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
59(8), P. 3178 - 3183
Published: Nov. 15, 2019
Abstract
Nickela‐electrooxidative
C−H
alkoxylations
with
challenging
secondary
alcohols
were
accomplished
in
a
fully
dehydrogenative
fashion,
thereby
avoiding
stoichiometric
chemical
oxidants,
H
2
as
the
only
byproduct.
The
nickela‐electrocatalyzed
oxygenation
proved
viable
various
(hetero)arenes,
including
naturally
occurring
alcohols,
without
racemization.
Detailed
mechanistic
investigation,
DFT
calculations
and
cyclovoltammetric
studies
of
well‐defined
activated
nickel(III)
intermediate,
suggest
an
oxidation‐induced
reductive
elimination
at
nickel(III).
ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(18), P. 10551 - 10558
Published: Aug. 17, 2020
Detailed
density
functional
theory
calculations
provide
valuable
insight
into
reactivity-controlling
factors
in
transition
metal-catalyzed
C–H
activation
by
carboxylate
assistance.
The
chelation-assisted
of
a
variety
arenes
3d
and
4d
metal
complexes
was
analyzed
means
bond
order
analysis
through
(DFT)
as
well
energy
decomposition
DLPNO–CCSD(T)
calculations,
thereby
providing
in-depth
information
on
distinct
electronic
influences
the
key
state
demonstrating
preferred
base-assisted
internal
electrophilic
substitution
(BIES)
rather
than
concerted
metalation-deprotonation
(CMD)
pathway.
