ACS Catalysis,
Год журнала:
2023,
Номер
13(11), С. 7310 - 7321
Опубликована: Май 15, 2023
Anilines
are
important
moieties
in
organic
chemistry,
pharmaceuticals,
and
materials
science.
Although
para-selective
functionalization
of
anilides
tertiary
anilines
is
well
established,
unprotected
have
posed
a
challenge.
Herein,
we
report
visible-light-mediated
Ru(II)-catalyzed
para-alkylation
anilines.
The
distinct
Ru(II)–aniline
complex
enabled
the
reaction
to
proceed
with
extremely
high
efficiency
(2
h)
under
mild
conditions.
good
functional
group
tolerance
allowed
late-stage
even
aggregation-induced
emission
luminogen
labeling
natural
products
drugs.
A
mechanistic
investigation
suggests
that
crucial
for
both
triggering
controlling
para-selectivity.
Accounts of Chemical Research,
Год журнала:
2019,
Номер
53(1), С. 84 - 104
Опубликована: Дек. 19, 2019
To
improve
the
efficacy
of
molecular
syntheses,
researchers
wish
to
capitalize
upon
selective
modification
otherwise
inert
C-H
bonds.
The
past
two
decades
have
witnessed
considerable
advances
in
coordination
chemistry
that
set
stage
for
transformative
tools
functionalizations.
Particularly,
oxidative
C-H/C-H
and
C-H/Het-H
transformations
gained
major
attention
because
they
avoid
all
elements
substrate
prefunctionalization.
Despite
advances,
activations
been
dominated
by
precious
transition
metal
catalysts
based
on
palladium,
ruthenium,
iridium,
rhodium,
thus
compromising
sustainable
nature
overall
activation
approach.
same
holds
true
predominant
use
stoichiometric
chemical
oxidants
regeneration
active
catalyst,
prominently
featuring
hypervalent
iodine(III),
copper(II),
silver(I)
oxidants.
Thereby,
quantities
undesired
byproducts
are
generated,
which
preventive
applications
scale.
In
contrast,
elegant
merger
homogeneous
metal-catalyzed
with
electrosynthesis
bears
unique
power
achieve
outstanding
levels
oxidant
resource
economy.
Thus,
contrast
classical
electrosyntheses
control,
metalla-electrocatalysis
huge
largely
untapped
potential
unmet
site
selectivities
means
catalyst
control.
While
indirect
electrolysis
using
palladium
complexes
has
realized,
less
toxic
expensive
base
feature
distinct
beneficial
assets
toward
this
Account,
I
summarize
emergence
electrocatalyzed
earth-abundant
3d
metals
beyond,
a
topical
focus
contributions
from
our
laboratories
through
November
2019.
cobalt
electrocatalysis
was
identified
as
particularly
powerful
platform
wealth
transformations,
including
oxygenations
nitrogenations
well
alkynes,
alkenes,
allenes,
isocyanides,
carbon
monoxide,
among
others.
As
complementary
tools,
nickel,
copper,
very
recently
iron
devised
metalla-electrocatalyzed
activations.
Key
success
were
detailed
mechanistic
insights,
oxidation-induced
reductive
elimination
scenarios.
Likewise,
development
methods
make
weak
O-coordination
benefited
crucial
insights
into
catalyst's
modes
action
experiment,
operando
spectroscopy,
computation.
Overall,
thereby
syntheses
These
electrooxidative
frequently
characterized
improved
chemoselectivities.
Hence,
ability
dial
redox
at
minimum
level
required
desired
transformation
renders
an
ideal
functionalization
structurally
complex
molecules
sensitive
functional
groups.
This
strategy
was,
inter
alia,
successfully
applied
scale-up
continuous
flow
step-economical
assembly
polycyclic
aromatic
hydrocarbons.
Chemical Reviews,
Год журнала:
2021,
Номер
122(3), С. 3180 - 3218
Опубликована: Ноя. 19, 2021
Synthetic
organic
electrosynthesis
has
grown
in
the
past
few
decades
by
achieving
many
valuable
transformations
for
synthetic
chemists.
Although
electrocatalysis
been
popular
improving
selectivity
and
efficiency
a
wide
variety
of
energy-related
applications,
last
two
decades,
there
much
interest
to
develop
conceptually
novel
transformations,
selective
functionalization,
sustainable
reactions.
This
review
discusses
recent
advances
combination
electrochemistry
homogeneous
transition-metal
catalysis
synthesis.
The
enabling
mechanistic
studies
are
presented
alongside
advantages
as
well
future
directions
address
challenges
metal-catalyzed
electrosynthesis.
Chemical Reviews,
Год журнала:
2023,
Номер
123(19), С. 11269 - 11335
Опубликована: Сен. 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.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(21)
Опубликована: Март 20, 2023
Metalla-electrocatalyzed
C-H
oxygenation
represents
one
of
the
most
straightforward
and
sustainable
approaches
to
access
valuable
oxygenated
molecules.
Despite
significant
advances,
development
enantioselective
electrochemical
reaction
is
very
challenging
remains
elusive.
Herein,
we
described
first
CoII
-catalyzed
alkoxylation.
A
broad
range
enantioenriched
alkoxylated
phosphinamides
were
obtained
in
good
yields
with
excellent
enantioselectivities
(up
98
%
yield
>99
ee).
An
unusual
cobalt(III)
alcohol
complex
was
prepared
fully
characterized,
which
proven
be
a
key
intermediate
this
alkoxylation
reaction.
Mechanistic
studies
revealed
that
oxidation
CoIII
CoIV
facilitated
by
base
whole
process
proceeded
through
cobalt(III/IV/II)
catalytic
cycle.
Angewandte Chemie International Edition,
Год журнала:
2020,
Номер
59(26), С. 10316 - 10320
Опубликована: Март 10, 2020
Abstract
A
mild
visible‐light‐induced
Pd‐catalyzed
intramolecular
C−H
arylation
of
amides
is
reported.
The
method
operates
by
cleavage
a
C(sp
2
)−O
bond,
leading
to
hybrid
aryl
Pd‐radical
intermediates.
following
1,5‐hydrogen
atom
translocation,
cyclization,
and
rearomatization
steps
lead
valuable
oxindole
isoindoline‐1‐one
motifs.
Notably,
this
provides
access
products
with
readily
enolizable
functional
groups
that
are
incompatible
traditional
conditions.
Angewandte Chemie International Edition,
Год журнала:
2019,
Номер
59(8), С. 3184 - 3189
Опубликована: Ноя. 28, 2019
The
catalytic
generation
of
hypervalent
iodine(III)
reagents
by
anodic
electrooxidation
was
orchestrated
towards
an
unprecedented
electrocatalytic
C-H
oxygenation
weakly
coordinating
aromatic
amides
and
ketones.
Thus,
quantities
iodoarenes
in
concert
with
amounts
ruthenium(II)
complexes
set
the
stage
for
versatile
activations
ample
scope
high
functional
group
tolerance.
Detailed
mechanistic
studies
experiment
computation
substantiate
role
iodoarene
as
electrochemically
relevant
species
oxygenations
electricity
a
sustainable
oxidant
molecular
hydrogen
sole
by-product.
para-Selective
likewise
proved
viable
absence
directing
groups.
