Chemical Science,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 27, 2024
A
palladium-catalysed
asymmetric
auto-tandem
reaction
between
4-alken-2-ynyl
carbonates
and
diverse
ortho-functionalized
activated
alkenes
is
reported,
giving
complex
frameworks
in
moderate
yields
with
excellent
chemo-,
regio-
stereoselectivity.
Accounts of Chemical Research,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 13, 2024
ConspectusElectrochemistry
has
been
used
as
a
tool
to
drive
chemical
reactions
for
more
than
two
centuries.
With
the
help
of
an
electrode
and
power
source,
chemists
are
provided
with
system
whose
potential
can
be
precisely
dialed
in.
The
theoretically
infinite
redox
range
renders
electrochemistry
capable
oxidizing
or
reducing
some
most
tenacious
compounds.
Indeed,
electroreduction
offers
alternative
generating
highly
active
intermediates
from
electrophiles
(e.g.,
halides,
alkenes,
etc.)
in
organic
synthesis,
which
untouchable
traditional
reduction
methods.
Meanwhile,
reductive
coupling
extensively
utilized
both
industrial
academic
settings
due
their
ability
swiftly,
accurately,
effectively
construct
C–C
C–X
bonds,
present
innovative
approaches
synthesizing
complex
molecules.
Nonetheless,
its
application
is
constrained
by
several
inherent
limitations:
(a)
requirement
stoichiometric
quantities
agents,
(b)
scarce
activation
strategies
inert
substrates
high
potentials,
(c)
incomplete
mechanistic
elucidation,
(d)
challenges
isolation
intermediates.
merging
represents
attractive
approach
address
above
limitations
synthesis
seen
increasing
use
synthetic
community
over
past
few
years.Since
2020,
our
group
dedicated
developing
electroreductive
cross-coupling
using
readily
available
small
molecules,
such
arenes,
CO2,
D2O,
value-added
products.
Electroreductive
chemistry
versatile
powerful
capacity
precise
selectivity
control,
allowed
us
develop
three
electrochemical
modes
lab:
(1)
An
economically
advantageous
direct
(EDR)
strategy
that
emphasizes
efficiency,
achieves
atom
utilization,
minimizes
unnecessary
atomic
waste.
(2)
A
class
organo-mediated
(EOMR)
methods
controlling
reaction
pathways.
This
allows
modulation
processes
enhance
efficiency
selectivity.
(3)
metal-catalyzed
(EMCR)
method
enables
selective
functionalization
specific
bonds
functional
groups
under
mild
conditions,
thereby
occurrence
side
reactions.
We
commenced
studies
establishing
organic-mediator-promoted
carboxylation
aryl
alkyl
halides.
was
then
employed
arylcarboxylation
simple
styrenes
halides
manner.
electrolysis
arenes
epoxides
CO2
carboxyl
source
achieved.
Moreover,
through
adjustment
we
successfully
accomplished
deuteration
olefins,
unactivated
enabling
efficient
formation
D-labeled
Finally,
building
on
previous
understanding
developed
series
alkylation
enable
C(sp3)–C(sp3)
Beilstein Journal of Organic Chemistry,
Год журнала:
2024,
Номер
20, С. 2500 - 2566
Опубликована: Окт. 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.
Chemical Society Reviews,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 1, 2025
This
review
highlights
organo-mediators
that
enable
electrochemical
reactions
via
outer-sphere
electron
transfer
(ET),
offering
advantages
such
as
availability,
tunability,
and
simplified
post-processing
compared
to
direct
electrolysis.
This
paper
reviews
progress
in
the
photochemical/electrochemical
construction
of
heterocyclic
compounds
using
CO
2
,
differentiating
between
various
reaction
types
and
elucidating
their
underlying
mechanisms
as
well
potential
applications.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
64(1)
Опубликована: Ноя. 7, 2024
Abstract
Precise
synthesis
of
carboxylic
acids
via
catalytic
carboxylation
with
CO
2
is
highly
appealing.
Although
considerable
advancements
have
been
achieved
in
difunctionalizing
unsaturated
hydrocarbons,
the
asymmetric
variants
are
conspicuously
underdeveloped,
particularly
addressing
axially
chiral
alkenes.
Herein,
we
report
first
atroposelective
alkynes
.
A
variety
valuable
obtained
good
yields
and
high
chemo‐,
regio‐,
Z/E
enantio‐selectivities.
Notably,
an
unexpected
anti
‐selective
carbo‐carboxylation
observed
sp
‐hybrid
carbo‐electrophile‐initiated
reductive
alkynes.
Mechanistic
studies
including
DFT
calculation
elucidate
origin
induction
‐selectivity
vinyl‐carboxylation