Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(42), P. 19456 - 19465
Published: Oct. 5, 2022
Highly
chemo-
and
regioselective
semihydrogenation
of
alkynes
is
significant
challenging
for
the
synthesis
functionalized
alkenes.
Here,
a
sequential
self-template
method
used
to
synthesize
amorphous
palladium
sulfide
nanocapsules
(PdSx
ANCs),
which
enables
electrocatalytic
terminal
in
H2O
with
excellent
tolerance
easily
reducible
groups
(e.g.,
C–I/Br/Cl,
C═O)
metal
center
deactivating
skeletons
quinolyl,
carboxyl,
nitrile).
Mechanistic
studies
demonstrate
that
specific
σ-alkynyl
adsorption
via
carbon
negligible
alkene
on
isolated
Pd2+
sites
ensure
successful
various
alkenes
outstanding
time-irrelevant
selectivity
wide
potential
range.
The
key
hydrogen
radical
intermediates
are
validated
by
electron
paramagnetic
resonance
high-resolution
mass
spectrometry.
Gram-scale
4-bromostyrene
expedient
preparation
deuterated
precursors
drugs
D2O
show
promising
applications.
Impressively,
PdSx
ANCs
can
be
applied
prevailing
thermocatalytic
alkyne
using
H2.
Chemical Reviews,
Journal Year:
2022,
Volume and Issue:
122(6), P. 6634 - 6718
Published: Feb. 18, 2022
Organic
compounds
labeled
with
hydrogen
isotopes
play
a
crucial
role
in
numerous
areas,
from
materials
science
to
medicinal
chemistry.
Indeed,
while
the
replacement
of
by
deuterium
gives
rise
improved
absorption,
distribution,
metabolism,
and
excretion
(ADME)
properties
drugs
enables
preparation
internal
standards
for
analytical
mass
spectrometry,
use
tritium-labeled
is
key
technique
all
along
drug
discovery
development
pharmaceutical
industry.
For
these
reasons,
interest
new
methodologies
isotopic
enrichment
organic
molecules
extent
their
applications
are
equally
rising.
In
this
regard,
Review
intends
comprehensively
discuss
developments
area
over
last
years
(2017–2021).
Notably,
besides
fundamental
isotope
exchange
(HIE)
reactions
isotopically
analogues
common
reagents,
plethora
reductive
dehalogenative
deuteration
techniques
other
transformations
incorporation
emerging
now
part
labeling
toolkit.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(16), P. 7206 - 7237
Published: Jan. 1, 2022
This
review
covers
the
recent
progress
in
electro-/photo-catalytic
alkene-derived
radical
cation
chemistry
for
organic
synthesis,
including
synthetic
strategies,
plausible
mechanisms
and
further
research
outlook.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(47), P. 21170 - 21175
Published: Aug. 10, 2020
We
reported
a
selective
semihydrogenation
(deuteration)
of
numerous
terminal
and
internal
alkynes
using
H2
O
(D2
O)
as
the
H
(D)
source
over
Pd-P
alloy
cathode
at
lower
potential.
P-doping
caused
enhanced
specific
adsorption
promoted
intrinsic
activity
for
producing
adsorbed
atomic
hydrogen
(H*ads
)
from
water
electrolysis.
The
could
be
accomplished
potential
with
up
to
99
%
selectivity
78
Faraday
efficiency
alkene
products,
outperforming
pure
Pd
commercial
Pd/C.
This
electrochemical
might
proceed
via
H*ads
addition
pathway
rather
than
proton-coupled
electron
transfer
process.
decreased
amount
more
preferential
C≡C
π
bond
C=C
moiety
resulted
in
excellent
selectivity.
method
was
capable
mono-,
di-,
tri-deuterated
alkenes
deuterium
incorporation.
eScience,
Journal Year:
2022,
Volume and Issue:
2(3), P. 243 - 277
Published: April 23, 2022
Compared
with
general
redox
chemistry,
electrochemistry
using
the
electron
as
a
potent,
controllable,
yet
traceless
alternative
to
chemical
oxidants/reductants
usually
offers
more
sustainable
options
for
achieving
selective
organic
synthesis.
With
its
environmentally
benign
features
gradually
being
uncovered
and
studied,
electrosynthesis
is
currently
undergoing
revival
becoming
rapidly
growing
area
within
synthetic
community.
Among
electrochemical
transformations,
anodically
enabled
ones
have
been
far
extensively
exploited
than
those
driven
by
cathodic
reduction,
although
both
approaches
are
conceptually
attractive.
To
stimulate
development
of
cathodically
reactions,
this
review
summarizes
recently
developed
reductive
electrosynthetic
protocols,
discussing
highlighting
reaction
features,
substrate
scopes,
applications,
plausible
mechanisms
reveal
recent
trends
in
area.
Herein,
reduction-enabled
preparative
transformations
categorized
into
four
types:
reduction
(1)
unsaturated
hydrocarbons,
(2)
heteroatom-containing
carbon-based
systems,
(3)
saturated
C-hetero
or
C–C
polar/strained
bonds,
(4)
hetero-hetero
linkages.
Apart
from
net
electroreductive
few
examples
photo-electrosynthesis
well
paired
electrolysis
also
introduced,
which
offer
opportunities
overcome
certain
limitations
improve
versatility.
The
electrochemically
driven,
transition
metal-catalyzed
cross-couplings
that
comprehensively
discussed
several
other
reviews
not
included
here.
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.
Nature Communications,
Journal Year:
2022,
Volume and Issue:
13(1)
Published: June 30, 2022
Abstract
Herein,
a
facile
and
general
electroreductive
deuteration
of
unactivated
alkyl
halides
(X
=
Cl,
Br,
I)
or
pseudo-halides
OMs)
using
D
2
O
as
the
economical
deuterium
source
was
reported.
In
addition
to
primary
secondary
halides,
sterically
hindered
tertiary
chlorides
also
work
very
well,
affording
target
deuterodehalogenated
products
with
excellent
efficiency
incorporation.
More
than
60
examples
are
provided,
including
late-stage
dehalogenative
natural
products,
pharmaceuticals,
their
derivatives,
all
incorporation
(up
99%
D),
demonstrating
potential
utility
developed
method
in
organic
synthesis.
Furthermore,
does
not
require
external
catalysts
tolerates
high
current,
showing
possible
use
industrial
applications.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(15), P. 6291 - 6306
Published: Jan. 1, 2022
This
review
is
a
systematic
summary
of
radical
deuteration
with
four
reaction
types:
reductive
deuteration,
defunctionalization–deuteration,
hydrogen–deuterium
(H/D)
exchange
and
deuteroalkylation.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(11), P. 6516 - 6525
Published: March 13, 2023
Electrochemical
alkynol
semi-hydrogenation
has
emerged
as
a
sustainable
and
environmentally
benign
route
for
the
production
of
high-value
alkenols,
featuring
water
hydrogen
source
instead
H2.
It
is
highly
challenging
to
design
electrode-electrolyte
interface
with
efficient
electrocatalysts
their
matched
electrolytes
break
selectivity-activity
stereotype.
Here,
boron-doped
Pd
catalysts
(PdB)
surfactant-modified
are
proposed
enable
simultaneous
increase
in
alkenol
selectivity
conversion.
Typically,
compared
pure
commercial
Pd/C
catalysts,
PdB
catalyst
achieves
both
higher
turnover
frequency
(139.8
h-1)
specific
(above
90%)
2-methyl-3-butyn-2-ol
(MBY).
Quaternary
ammonium
cationic
surfactants
that
employed
electrolyte
additives
assembled
at
electrified
response
applied
bias
potential,
establishing
an
interfacial
microenvironment
can
facilitate
transfer
hinder
suitably.
Eventually
evolution
reaction
inhibited
promoted,
without
inducing
decrease
selectivity.
This
work
offers
distinct
perspective
on
creating
suitable
electrosynthesis.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(41)
Published: May 15, 2023
Catalytic
hydrogen
atom
transfer
from
metal-hydrides
to
alkenes
allows
feedstock
olefins
be
used
as
alkyl
radical
precursors.
The
chemoselectivity
of
this
process
makes
it
an
attractive
synthetic
tool
and
such
has
been
regularly
in
synthesis
complex
molecules.
However,
onwards
reactivity
is
limited
by
compatibility
with
the
conditions
which
form
key
metal-hydride
species.
Now,
through
merger
photocatalysis
or
electrochemistry,
milder
methods
are
emerging
can
unlock
entirely
new
offer
perspectives
on
expanding
these
unprecedented
directions.
This
review
outlines
most
recent
developments
electro-
photochemical
cobalt
catalysed
offers
suggestions
future
outlook.
