Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(33)
Published: June 11, 2022
Strained
rings
are
increasingly
important
for
the
design
of
pharmaceutical
candidates,
but
cross-coupling
strained
remains
challenging.
An
attractive,
underdeveloped,
approach
to
diverse
functionalized
carbocyclic
and
heterocyclic
frameworks
containing
all-carbon
quaternary
centers
is
coupling
abundant
strained-ring
carboxylic
acids
with
aryl
halides.
Herein
we
disclose
development
a
nickel-catalyzed
cross-electrophile
that
couples
variety
ring
N-hydroxyphthalimide
(NHP)
esters,
derived
from
acid
in
one
step,
various
heteroaryl
halides
under
reductive
conditions.
The
chemistry
enabled
by
discovery
methods
control
NHP
ester
reactivity,
tuning
solvent
or
using
modified
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
122(3), P. 3292 - 3335
Published: Dec. 17, 2021
Electrosynthesis
is
a
popular,
green
alternative
to
traditional
organic
methods.
Understanding
the
mechanisms
not
trivial
yet
necessary
optimize
reaction
processes.
To
this
end,
multitude
of
analytical
tools
available
identify
and
quantitate
products
intermediates.
The
first
portion
review
serves
as
guide
that
underscores
electrosynthesis
fundamentals,
including
instrumentation,
electrode
selection,
impacts
electrolyte
solvent,
cell
configuration,
methods
electrosynthesis.
Next,
broad
base
techniques
aid
in
mechanism
elucidation
are
covered
detail.
These
divided
into
electrochemical,
spectroscopic,
chromatographic,
microscopic,
computational.
Technique
selection
dependent
on
predicted
pathways
electrogenerated
Often,
combination
must
be
utilized
ensure
accuracy
proposed
model.
conclude,
future
prospects
aim
enhance
field
discussed.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(16), P. 6257 - 6265
Published: April 16, 2021
Simple
copper
salts
serve
as
catalysts
to
effect
C–X
bond-forming
reactions
in
some
of
the
most
utilized
transformations
synthesis,
including
oxidative
coupling
aryl
boronic
acids
and
amines.
However,
these
Chan–Lam
have
historically
relied
on
chemical
oxidants
that
limit
their
applicability
beyond
small-scale
synthesis.
Despite
success
replacing
strong
with
electrochemistry
for
a
variety
metal-catalyzed
processes,
electrooxidative
ligandless
are
plagued
by
slow
electron-transfer
kinetics,
irreversible
plating,
competitive
substrate
oxidation.
Herein,
we
report
implementation
substoichiometric
quantities
redox
mediators
address
limitations
Cu-catalyzed
electrosynthesis.
Mechanistic
studies
reveal
multiple
roles
(i)
rapidly
oxidizing
low-valent
Cu
intermediates,
(ii)
stripping
metal
from
cathode
regenerate
catalyst
active
Pt
surface
proton
reduction,
(iii)
providing
anodic
overcharge
protection
prevent
This
strategy
is
applied
aryl-,
heteroaryl-,
alkylamines
arylboronic
absence
oxidants.
Couplings
under
electrochemical
conditions
occur
higher
yields
shorter
reaction
times
than
conventional
air
provide
complementary
reactivity.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(20), P. 12617 - 12626
Published: Oct. 3, 2022
Nickel-catalyzed
reductive
cross-electrophile
coupling
reactions
are
becoming
increasingly
important
in
organic
synthesis,
but
application
at
scale
is
limited
by
three
interconnected
challenges:
a
reliance
on
amide
solvents
(complicated
workup,
regulated),
the
generation
of
stoichiometric
Zn
salts
isolation,
waste
disposal
issue),
and
mixing/activation
challenges
zinc
powder.
We
show
here
an
electrochemical
approach
that
addresses
these
issues:
reaction
works
acetonitrile
with
diisopropylethylamine
as
terminal
reductant
simple
undivided
cell
(graphite(+)/nickel
foam(-)).
The
utilizes
combination
two
ligands,
4,4'-di-
Advanced Science,
Journal Year:
2022,
Volume and Issue:
10(1)
Published: Nov. 18, 2022
Electro-organic
synthesis
has
attracted
a
lot
of
attention
in
pharmaceutical
science,
medicinal
chemistry,
and
future
industrial
applications
energy
storage
conversion.
To
date,
there
not
been
detailed
review
on
electro-organic
with
the
strategy
heterogeneous
catalysis.
In
this
review,
most
recent
advances
synthesizing
value-added
chemicals
by
catalysis
are
summarized.
An
overview
electrocatalytic
oxidation
reduction
processes
as
well
paired
electrocatalysis
is
provided,
anodic
alcohols
(monohydric
polyhydric),
aldehydes,
amines
discussed.
This
also
provides
in-depth
insight
into
cathodic
carboxylates,
carbon
dioxide,
CC,
C≡C,
reductive
coupling
reactions.
Moreover,
electro-synthesis
methods,
including
parallel
paired,
sequential
divergent
convergent
electrolysis,
Additionally,
strategies
developed
to
achieve
high
electrosynthesis
efficiency
associated
challenges
addressed.
It
believed
that
promising
direction
organic
electrochemistry,
offering
numerous
opportunities
develop
new
reaction
methods.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(33)
Published: June 11, 2022
Strained
rings
are
increasingly
important
for
the
design
of
pharmaceutical
candidates,
but
cross-coupling
strained
remains
challenging.
An
attractive,
underdeveloped,
approach
to
diverse
functionalized
carbocyclic
and
heterocyclic
frameworks
containing
all-carbon
quaternary
centers
is
coupling
abundant
strained-ring
carboxylic
acids
with
aryl
halides.
Herein
we
disclose
development
a
nickel-catalyzed
cross-electrophile
that
couples
variety
ring
N-hydroxyphthalimide
(NHP)
esters,
derived
from
acid
in
one
step,
various
heteroaryl
halides
under
reductive
conditions.
The
chemistry
enabled
by
discovery
methods
control
NHP
ester
reactivity,
tuning
solvent
or
using
modified
