Handbook of CH‐Functionalization,
Journal Year:
2022,
Volume and Issue:
unknown, P. 1 - 18
Published: Oct. 1, 2022
Abstract
This
article
summarizes
the
design
of
catalytic
systems
and
regioselective
CH
borylation
(hetero)aromatic
compounds
using
noncovalent
interactions,
such
as
hydrogen
bonding
Lewis
acid–base
interaction,
between
substrate
recognition
part
ligand
catalysts
functional
group
substrates.
Formal
meta‐selective
introduction
a
variety
groups
into
based
on
is
explained.
In
addition,
acceleration
reaction
expression
specificities
are
introduced.
summary
section,
recently
reported
reactions
interaction
method
several
reviews
accounts
cited.
Science,
Journal Year:
2022,
Volume and Issue:
375(6581), P. 658 - 663
Published: Feb. 10, 2022
Regioselective
functionalization
of
arenes
remains
a
challenging
problem
in
organic
synthesis.
Steric
interactions
are
often
used
to
block
sites
adjacent
given
substituent,
but
they
do
not
distinguish
the
remaining
remote
sites.
We
report
strategy
based
on
steric
control,
whereby
roof-like
ligand
protects
distant
para
site
addition
ortho
sites,
and
thereby
enables
selective
activation
meta
carbon-hydrogen
(C–H)
bonds
absence
or
substituents.
demonstrate
this
concept
for
iridium-catalyzed
-selective
borylation
various
monosubstituted
arenes,
including
complex
drug
molecules.
This
has
potential
expand
toolbox
C–H
bond
previously
nondifferentiable
reaction
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(45)
Published: June 7, 2023
C-H
activation
is
an
attractive
methodology
to
increase
molecular
complexity
without
requiring
substrate
prefunctionalization.
In
contrast
well-established
cross-coupling
methods,
less
explored
on
large
scales
and
its
use
in
the
production
of
pharmaceuticals
faces
substantial
hurdles.
However,
inherent
advantages,
such
as
shorter
synthetic
routes
simpler
starting
materials,
motivate
medicinal
chemists
process
overcome
these
challenges,
exploit
steps
for
synthesis
pharmaceutically
relevant
compounds.
this
review,
we
will
cover
examples
drugs/drug
candidates
where
has
been
implemented
a
preparative
scale
(range
between
355
mg
130
kg).
The
optimization
processes
be
described,
each
example
examined
terms
advantages
disadvantages,
providing
reader
with
in-depth
understanding
challenges
potential
methodologies
pharmaceuticals.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(31)
Published: May 31, 2022
Reversing
the
conventional
site-selectivity
of
C-H
activation
processes
provides
new
retrosynthetic
disconnections
to
otherwise
unreactive
bonds.
Here,
we
report
a
catalytic
system
based
on
palladium/norbornene
and
an
S,O-ligand
for
meta-C-H
arylation
aryl
ethers
that
significantly
outperforms
previously
reported
systems.
We
demonstrate
unique
ability
this
employ
alkoxyarene
substrates
bearing
electron
donating
withdrawing
substituents.
Additionally,
ortho-substituted
are
well
tolerated,
overcoming
"ortho
constraint",
which
is
necessity
have
meta-substituent
achieve
high
reaction
efficiency,
by
enlisting
novel
norbornene
mediators.
Remarkably,
first
time
monoarylation
alkoxyarenes
achieved
efficiently
enabling
subsequent
introduction
second,
different
coupling
partner
rapidly
furnish
unsymmetrical
terphenyls.
Further
insight
into
mechanism
was
isolation
characterization
some
Pd-complexes-before
after
meta
activation-prior
evaluation
their
respective
activities.
Chemistry - A European Journal,
Journal Year:
2022,
Volume and Issue:
28(39)
Published: May 7, 2022
A
palladium-catalyzed
[3+2]
annulation
of
substituted
benzoic
acids
with
maleimides
leading
to
tricyclic
heterocyclic
molecules
having
a
free
carboxylic
group
in
high
atom-
and
step-economical
manner
is
described.
The
reaction
proceeds
via
dual
C-H
bond
activation
such
as
C(sp3
)-H
at
the
benzylic
position
C(sp2
meta
aromatics.
An
external
ligand
(MPAA)
crucial
for
success
present
protocol.
Further,
decarboxylation
esterification
acid
observed
products
were
carried
out.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(21), P. 8402 - 8406
Published: Oct. 19, 2021
A
unified
method
for
direct
C4–H
halogenation
of
indoles
has
been
accomplished
with
the
assistance
anthranilic
acids
as
suitable
transient
directing
groups.
Exclusive
site
selectivity
(one
out
five
potential
reactive
sites)
well
good
functional
group
tolerance
was
obtained
to
install
three
kinds
halogen
atoms
(Cl,
Br
and
I,
respectively)
by
using
inexpensive
N-halosuccinimides
(NXS)
sources
under
mild
conditions.
Taking
advantage
rich
groups
in
product,
a
diversity
nitrogen-containing
heterocycles
were
facily
constructed
via
one-step
late-stage
derivations.
Asian Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
12(2)
Published: Oct. 19, 2022
Abstract
C−H
bond
functionalization
is
one
of
the
most
efficient
strategies
for
rapid
synthesis
cyclic
amines
containing
substituents
in
ring,
which
are
core
structures
many
bioactive
molecules.
However,
it
much
more
challenging
to
perform
this
strategy
on
remote
bonds
than
α
‐C−H
amines.
This
review
provides
a
comprehensive
overview
transition
metal‐free
methods
amines,
complementary
relying
metal
catalysis.
Selected
substrate
scope
and
discussion
reaction
mechanism
given
when
necessary.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(19), P. 3549 - 3554
Published: May 6, 2022
Herein,
the
first
catalytic
protocol
for
nickel-catalyzed
ortho
or
para
position
difluoromethylation
of
various
aromatic
amines
has
been
developed
with
assistance
a
bidentate
phosphine
ligand,
offering
an
invaluable
synthesis
means
to
construct
extensive
p-difluoromethylated
products
and
difluorooxindole
derivatives
significant
functional
fragments.
Furthermore,
gram-scale
reaction,
broad
substrate
scope,
excellent
functional-group
compatibility,
late-stage
pesticides,
even
formal
HDAC6
inhibitors
further
demonstrate
usefulness
this
method.
