Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: June 18, 2024
Abstract
Peptide
aldehydes
are
crucial
biomolecules
essential
to
various
biological
systems,
driving
a
continuous
demand
for
efficient
synthesis
methods.
Herein,
we
develop
metal-free,
facile,
and
biocompatible
strategy
direct
electrochemical
of
unnatural
peptide
aldehydes.
This
electro-oxidative
approach
enabled
step-
atom-economical
ring-opening
via
C‒N
bond
cleavage,
allowing
homoproline-specific
diversification
expansion
substrate
scope
include
amides,
esters,
cyclic
amines
sizes.
The
remarkable
efficacy
the
electro-synthetic
protocol
set
stage
modification
assembly
linear
macrocyclic
peptides
using
concise
synthetic
sequence
with
racemization-free
conditions.
Moreover,
combination
experiments
density
functional
theory
(DFT)
calculations
indicates
that
different
N
-acyl
groups
play
decisive
role
in
reaction
activity.
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.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(12), P. 6944 - 6952
Published: March 15, 2023
Enantioselective
metallaphotoredox
catalysis,
which
combines
photoredox
catalysis
and
asymmetric
transition-metal
has
become
an
effective
approach
to
achieve
stereoconvergence
under
mild
conditions.
Although
many
impressive
synthetic
approaches
have
been
developed
access
central
chirality,
the
construction
of
axial
chirality
by
still
remains
underexplored.
Herein,
we
report
two
visible
light-induced
cobalt-catalyzed
reductive
couplings
biaryl
dialdehydes
synthesize
axially
chiral
aldehydes
(60
examples,
up
98%
yield,
>19:1
dr,
>99%
ee).
This
protocol
shows
good
functional
group
tolerance,
broad
substrate
scope,
excellent
diastereo-
enantioselectivity.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(34), P. 18753 - 18759
Published: Aug. 15, 2023
The
asymmetric
difunctionalization
of
alkenes,
a
method
transforming
readily
accessible
alkenes
into
enantioenriched
chiral
structures
high
value,
has
long
been
focal
point
organic
synthesis.
Despite
tremendous
efforts
in
this
domain,
it
remains
considerable
challenge
to
devise
enantioselective
oxidative
dicarbofunctionalization
even
though
these
transformations
can
utilize
stable
and
unfunctionalized
functional
group
donors.
In
context,
we
report
herein
photoelectrocatalytic
for
the
heteroarylcyanation
aryl
which
employs
heteroarenes
through
C-H
functionalization.
photoelectrochemical
catalysis
(PEAC)
combines
photoredox
electrocatalysis
facilitate
formation
two
C-C
bonds
operating
via
hydrogen
(H2)
evolution
obviating
need
external
chemical
oxidants.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
52(23), P. 8106 - 8125
Published: Jan. 1, 2023
This
tutorial
review
delves
into
the
unique
advantages
of
electrochemistry
in
context
asymmetric
catalysis,
first
providing
a
brief
introduction
to
electrosynthesis,
then
exploring
representative
case
studies
with
mechanistic
focus.
European Journal of Organic Chemistry,
Journal Year:
2023,
Volume and Issue:
26(21)
Published: April 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,
Journal Year:
2023,
Volume and Issue:
62(24)
Published: April 1, 2023
Due
to
the
intrinsic
inertness
of
alkanes,
strong
oxidative
conditions
are
typically
required
enable
their
C(sp3
)-H
functionalization.
Herein,
a
paired
electrocatalysis
strategy
was
developed
by
integrating
catalysis
with
reductive
in
one
cell
without
interference,
which
earth-abundant
iron
and
nickel
employed
as
anodic
cathodic
catalysts,
respectively.
This
approach
lowers
previously
high
oxidation
potential
for
alkane
activation,
enabling
electrochemical
functionalization
at
ultra-low
≈0.25
V
vs.
Ag/AgCl
under
mild
conditions.
Structurally
diverse
alkenes,
including
challenging
all-carbon
tetrasubstituted
olefins,
can
be
accessed
using
readily
available
alkenyl
electrophiles.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(50)
Published: Aug. 22, 2023
Abstract
Organic
electrosynthesis
has
consistently
aroused
significant
interest
within
both
academic
and
industrial
spheres.
Despite
the
considerable
progress
achieved
in
this
field,
majority
of
electrochemical
transformations
have
been
conducted
through
utilization
direct‐current
(DC)
electricity.
In
contrast,
application
alternating
current
(AC),
characterized
by
its
polarity‐alternating
nature,
remains
infancy
sphere
organic
synthesis,
primarily
due
to
absence
a
comprehensive
theoretical
framework.
This
minireview
offers
an
overview
recent
advancements
AC‐driven
seeks
elucidate
differences
between
DC
AC
electrolytic
methodologies
probing
into
their
underlying
physical
principles.
These
encompass
ability
preclude
deposition
metal
catalysts,
precision
modulating
oxidation
reduction
intensities,
mitigation
mass
transfer
processes.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(2), P. 1522 - 1531
Published: Jan. 3, 2024
The
development
of
a
reliable
strategy
for
stereodivergent
radical
reactions
that
allows
convenient
access
to
all
stereoisomers
homocoupling
adducts
with
multiple
stereogenic
centers
remains
an
unmet
goal
in
organic
synthesis.
Herein,
we
describe
dual-catalyzed
electrooxidative
C(sp3)–H/C(sp3)–H
complete
absolute
and
relative
stereocontrol
the
synthesis
molecules
contiguous
quaternary
stereocenters
general
predictable
manner.
reaction
is
achieved
by
synergistically
utilizing
two
distinct
chiral
catalysts
convert
identical
racemic
substrates
into
inherently
distinctive
reactive
intermediates,
dictate
enantioselective
addition,
allow
full
complement
stereoisomeric
products
via
simple
catalyst
permutation.
successful
execution
dual-electrocatalytic
programmed
activation
provides
significant
conceptual
advantage
will
serve
as
useful
foundation
further
research
cooperative
stereocontrolled
transformations
diversity-oriented
