Chemical Reviews,
Год журнала:
2016,
Номер
117(4), С. 2910 - 3043
Опубликована: Окт. 6, 2016
This
review
focuses
on
the
postfunctionalization
of
porphyrins
and
related
compounds
through
catalytic
stoichiometric
organometallic
methodologies.
The
employment
reactions
has
become
common
in
porphyrin
synthesis.
Palladium-catalyzed
cross-coupling
are
now
standard
techniques
for
constructing
carbon-carbon
bonds
In
addition,
iridium-
or
palladium-catalyzed
direct
C-H
functionalization
is
emerging
as
an
efficient
way
to
install
various
substituents
onto
porphyrins.
Furthermore,
copper-mediated
Huisgen
cycloaddition
reaction
a
frequent
strategy
incorporate
units
into
functional
molecules.
use
these
techniques,
along
with
traditional
synthesis,
allows
chemists
construct
wide
range
highly
elaborated
complex
architectures.
Chemical Reviews,
Год журнала:
2020,
Номер
120(4), С. 1981 - 2048
Опубликована: Янв. 22, 2020
In
this
contribution,
we
provide
a
comprehensive
overview
of
C-H
activation
methods
promoted
by
NHC-transition
metal
complexes,
covering
the
literature
since
2002
(the
year
first
report
on
metal-NHC-catalyzed
activation)
through
June
2019,
focusing
both
NHC
ligands
and
methods.
This
review
covers
reactions
catalyzed
group
8
to
11
NHC-metal
complexes.
Through
discussing
role
in
promoting
challenging
methods,
reader
is
provided
with
an
important
area
its
crucial
forging
carbon-carbon
carbon-heteroatom
bonds
directly
engaging
ubiquitous
bonds.
ACS Catalysis,
Год журнала:
2018,
Номер
8(8), С. 7179 - 7189
Опубликована: Июнь 19, 2018
Electrochemical
transition
metal
catalysis
is
a
powerful
strategy
for
organic
synthesis
because
it
obviates
the
use
of
stoichiometric
chemical
oxidants
and
reductants.
C–H
bond
functionalization
offers
variety
useful
conversions
simple
ubiquitous
molecules
into
diverse
functional
groups
in
single
synthetic
operation.
This
review
summarizes
recent
progress
merging
electrochemistry
with
metal-catalyzed
functionalization,
specifically
C–C,
C–X
(halogen),
C–O,
C–P,
C–N
formation.
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:
2016,
Номер
117(4), С. 2910 - 3043
Опубликована: Окт. 6, 2016
This
review
focuses
on
the
postfunctionalization
of
porphyrins
and
related
compounds
through
catalytic
stoichiometric
organometallic
methodologies.
The
employment
reactions
has
become
common
in
porphyrin
synthesis.
Palladium-catalyzed
cross-coupling
are
now
standard
techniques
for
constructing
carbon-carbon
bonds
In
addition,
iridium-
or
palladium-catalyzed
direct
C-H
functionalization
is
emerging
as
an
efficient
way
to
install
various
substituents
onto
porphyrins.
Furthermore,
copper-mediated
Huisgen
cycloaddition
reaction
a
frequent
strategy
incorporate
units
into
functional
molecules.
use
these
techniques,
along
with
traditional
synthesis,
allows
chemists
construct
wide
range
highly
elaborated
complex
architectures.
