Science,
Год журнала:
2016,
Номер
353(6304), С. 1144 - 1147
Опубликована: Сен. 8, 2016
Primary
and
N
-alkyl
arylamine
motifs
are
key
functional
groups
in
pharmaceuticals,
agrochemicals,
materials,
as
well
bioactive
natural
products.
However,
there
is
a
dearth
of
generally
applicable
methods
for
the
direct
replacement
aryl
hydrogens
with
NH
2
/NH(alkyl)
moieties.
Here,
we
present
mild
dirhodium-catalyzed
C-H
amination
conversion
structurally
diverse
monocyclic
fused
aromatics
to
corresponding
primary
arylamines
using
/NH(alkyl)-
O
-(sulfonyl)hydroxylamines
aminating
agents;
relatively
weak
RSO
O-N
bond
functions
an
internal
oxidant.
The
methodology
operationally
simple,
scalable,
fast
at
or
below
ambient
temperature,
furnishing
moderate-to-good
yields
good
regioselectivity.
It
can
be
readily
extended
synthesis
-heterocycles.
Chemical Reviews,
Год журнала:
2016,
Номер
117(13), С. 8754 - 8786
Опубликована: Дек. 2, 2016
This
Review
summarizes
the
advancements
in
Pd-catalyzed
C(sp3)-H
activation
via
various
redox
manifolds,
including
Pd(0)/Pd(II),
Pd(II)/Pd(IV),
and
Pd(II)/Pd(0).
While
few
examples
have
been
reported
of
alkane
C-H
bonds,
many
activation/C-C
C-heteroatom
bond
forming
reactions
developed
by
use
directing
group
strategies
to
control
regioselectivity
build
structural
patterns
for
synthetic
chemistry.
A
number
mono-
bidentate
ligands
also
proven
be
effective
accelerating
directed
weakly
coordinating
auxiliaries,
which
provides
great
opportunities
reactivity
selectivity
(including
enantioselectivity)
functionalization
reactions.
Chemical Society Reviews,
Год журнала:
2016,
Номер
45(10), С. 2900 - 2936
Опубликована: Янв. 1, 2016
C–H
Activation
reactions
that
proceed
under
mild
conditions
are
more
attractive
for
applications
in
complex
molecule
synthesis.
Mild
transformations
reported
since
2011
reviewed
and
the
different
concepts
strategies
have
enabled
their
mildness
discussed.
Chemical Society Reviews,
Год журнала:
2015,
Номер
45(3), С. 546 - 576
Опубликована: Окт. 28, 2015
The
advent
of
modern
C-H
functionalization
chemistries
has
enabled
medicinal
chemists
to
consider
a
synthetic
strategy,
late
stage
(LSF),
which
utilizes
the
bonds
drug
leads
as
points
diversification
for
generating
new
analogs.
LSF
approaches
offer
promise
rapid
exploration
structure
activity
relationships
(SAR),
generation
oxidized
metabolites,
blocking
metabolic
hot
spots
and
preparation
biological
probes.
This
review
details
toolbox
intermolecular
with
proven
applicability
drug-like
molecules,
classified
by
regioselectivity
patterns,
gives
guidance
on
how
systematically
develop
strategies
using
these
patterns
other
considerations.
In
addition,
number
examples
illustrate
have
been
used
impact
actual
discovery
chemical
biology
efforts.
Chemical Society Reviews,
Год журнала:
2018,
Номер
47(17), С. 6603 - 6743
Опубликована: Янв. 1, 2018
The
present
review
is
devoted
to
summarizing
the
recent
advances
(2015-2017)
in
field
of
metal-catalysed
group-directed
C-H
functionalisation.
In
order
clearly
showcase
molecular
diversity
that
can
now
be
accessed
by
means
directed
functionalisation,
whole
organized
following
directing
groups
installed
on
a
substrate.
Its
aim
comprehensive
reference
work,
where
specific
group
easily
found,
together
with
transformations
which
have
been
carried
out
it.
Hence,
primary
format
this
schemes
accompanied
concise
explanatory
text,
are
ordered
sections
according
their
chemical
structure.
feature
typical
substrates
used,
products
obtained
as
well
required
reaction
conditions.
Importantly,
each
example
commented
respect
most
important
positive
features
and
drawbacks,
aspects
such
selectivity,
substrate
scope,
conditions,
removal,
greenness.
targeted
readership
both
experts
functionalisation
chemistry
(to
provide
overview
progress
made
last
years)
and,
even
more
so,
all
organic
chemists
who
want
introduce
way
thinking
for
design
straightforward,
efficient
step-economic
synthetic
routes
towards
molecules
interest
them.
Accordingly,
should
particular
also
scientists
from
industrial
R&D
sector.
overall
goal
promote
application
reactions
outside
research
dedicated
method
development
establishing
it
valuable
archetype
contemporary
R&D,
comparable
role
cross-coupling
play
date.
Chemical Reviews,
Год журнала:
2020,
Номер
120(3), С. 1788 - 1887
Опубликована: Янв. 6, 2020
During
the
past
decades,
synthetic
organic
chemistry
discovered
that
directing
group
assisted
C–H
activation
is
a
key
tool
for
expedient
and
siteselective
construction
of
C–C
bonds.
Among
various
strategies,
bidentate
groups
are
now
recognized
as
one
most
efficient
devices
selective
functionalization
certain
positions
due
to
fact
its
metal
center
permits
fine,
tunable,
reversible
coordination.
The
family
permit
types
assistance
be
achieved,
such
N,N-dentate,
N,O-dentate,
N,S-dentate
auxiliaries,
which
categorized
based
on
coordination
site.
In
this
review,
we
broadly
discuss
bond
reactions
formation
bonds
with
aid
groups.
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.
Angewandte Chemie International Edition,
Год журнала:
2016,
Номер
55(37), С. 11000 - 11019
Опубликована: Июнь 22, 2016
The
exponential
increase
in
the
number
of
catalytic
transformations
that
involve
a
metal-promoted
activation
hitherto
considered
inert
C-H
bonds
is
promoting
fundamental
change
field
synthetic
chemistry.
Although
most
reactions
involving
activations
consist
simple
functionalizations
or
additions,
recent
years
have
witnessed
an
upsurge
related
can
be
formally
as
cycloaddition
processes.
These
are
particularly
appealing
from
perspective
because
they
allow
conversion
readily
available
substrates
into
highly
valuable
cyclic
products
rapid
and
sustainable
manner.
In
many
cases,
these
annulations
formation
metallacyclic
intermediates
resemble
those
proposed
for
standard
metal-catalyzed
cycloadditions
unsaturated
precursors.
ACS Catalysis,
Год журнала:
2015,
Номер
6(2), С. 610 - 633
Опубликована: Дек. 7, 2015
Transformations
of
aromatic
compounds
into
the
corresponding
amines,
amides,
and
imides
through
carbon–hydrogen
(C–H)
bond
functionalization
represent
one
most
step-
atom-economical
methods
for
synthesis
arylamine
compounds.
Because
arylamines
are
privileged
structures
in
materials-
biology-oriented
functional
molecules,
development
novel
efficient
synthetic
C–H
amination
has
received
significant
attention
from
a
wide
range
research
fields
including
materials
pharmaceuticals.
This
review
covers
recent
advances
catalytic
reactions.
An
array
recently
developed
new
reactions
categorized
by
nature
substrates:
(1)
5-membered
heteroarenes,
(2)
arenes
having
nitrogen
moiety
molecule
(intramolecular
amination),
(3)
directing
group,
(4)
simple
with
excess
amounts,
(5)
as
limiting
reagents.
Chemical Reviews,
Год журнала:
2017,
Номер
117(13), С. 9302 - 9332
Опубликована: Апрель 26, 2017
Azines,
which
are
six-membered
aromatic
compounds
containing
one
or
more
nitrogen
atoms,
serve
as
ubiquitous
structural
cores
of
species
with
important
applications
in
biological
and
materials
sciences.
Among
a
variety
synthetic
approaches
toward
azines,
C-H
functionalization
represents
the
most
rapid
atom-economical
transformation,
it
is
advantageous
for
late-stage
azine-containing
functional
molecules.
Since
azines
have
several
bonds
different
reactivities,
development
new
reactions
that
allow
regioselective
fashion
has
comprised
central
issue.
This
review
describes
recent
advances
categorized
follows:
(1)
SNAr
reactions,
(2)
radical
(3)
deprotonation/functionalization,
(4)
metal-catalyzed
reactions.
Advanced Synthesis & Catalysis,
Год журнала:
2017,
Номер
359(8), С. 1245 - 1262
Опубликована: Март 16, 2017
Abstract
High‐valent
(pentamethylcyclopentadienyl)cobalt(III)
[Cp*Co(III)]
catalysts
were
found
as
inexpensive
alternatives
to
(pentamethylcyclopentadienyl)rhodium(III)
[Cp*Rh(III)]
in
the
field
of
C—H
bond
functionalization,
and
applied
a
variety
transformations.
In
this
review,
after
discovery
early
examples
Cp*Co(III)‐catalyzed
functionalization
are
summarized,
unique
reactivity
selectivity
Cp*Co(III)
differences
between
cobalt
rhodium
catalysis
intensively
discussed.
Such
assumed
be
caused
by
lower
electronegativity,
hard
nature,
smaller
ionic
radius
cobalt.
magnified
image
