Handbook of CH‐Functionalization,
Journal Year:
2022,
Volume and Issue:
unknown, P. 1 - 39
Published: Oct. 2, 2022
Abstract
Rhodium
complexes
are
exceptionally
significant
in
homogeneous
catalysis.
The
synthetic
community
observed
the
rapid
burgeoning
of
such
rhodium
catalysis
since
discovery
Wilkinson's
catalyst.
Rhodium‐catalyzed
tandem
C(sp
2
)H/C(sp
3
)H
activation
and
annulation
with
alkenes,
alkynes,
arenes,
other
reactive
partners
is
a
rapidly
growing
research
field
to
obtain
new
class
heterocycles
thereby
generates
potential
biologically
active
pharmacophores.
Superior
reactivity
catalysts
attributed
due
its
good
π‐acceptor
character
that
favors
CH
bond
reaction
substrates
containing
wide
range
directing
groups,
as
amides,
imines,
carboxylic
acid
(derivatives),
benzylic
alcohols,
ketones,
various
shown
efficiency
toward
befitting
partners;
even
undirected
activations
have
also
been
achieved.
This
article
provides
brief
account
recent
developments
rhodium‐catalyzed
activation/annulation
reactions
for
synthesis
classes
fused
cyclic
scaffolds
using
suitable
coupling
partners.
For
strategies,
different
types
cyclization
reactions,
namely,
oxidative,
redox‐neutral,
photoredox,
electrochemical
discussed.
In
addition,
enantioselective
annulated
molecules
chiral
has
highlighted.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(2), P. 124 - 141
Published: Jan. 10, 2023
Abstract
Transition‐metal‐catalyzed
oxidative
annulation
reactions
can
be
used
to
synthesize
various
benzo‐fused
oxygen‐
and
nitrogen‐containing
heterocyclic
compounds
from
benzoic
acids.
This
review
deals
with
publications
the
past
15
years
that
focus
on
modifications
of
reaction
conditions
variations
coupling
reagents
this
end,
as
well
development
methods
characterized
by
sustainability,
a
broad
range
substrates,
high
tolerance
functional
groups
in
constructing
skeletons
are
commonly
found
drugs
bioactive
molecules.
summarizes
categorizes
mechanisms
reagents.
magnified
image
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(19), P. 3341 - 3346
Published: May 5, 2023
Rh(III)-catalyzed
successive
C-H
activations
of
2-phenyl-3H-indoles
and
cyclization
cascades
with
diazo
compounds
were
developed
to
construct
highly
fused
indole
heteropolycycles
a
broad
range
substrates
good
yields.
In
particular,
this
transformation
included
two
unusual
[3+3]
[4+2]
sequential
cascades,
in
which
the
compound
played
different
role
processes,
while
simultaneously
forming
polycyclic
scaffold
new
quaternary
carbon
center.
Organic Letters,
Journal Year:
2021,
Volume and Issue:
23(20), P. 7888 - 7893
Published: Oct. 6, 2021
Given
their
omnipresence
in
natural
products
and
pharmaceuticals,
isochromenone
congeners
are
one
of
the
most
privileged
scaffolds
to
synthetic
chemists.
Disclosed
herein
is
a
dual
(ortho/meta)
C-H
C-C
activation
phenacyl
ammonium
salts
(acylammonium
as
traceless
directing
group)
toward
annulation
with
propargylic
alcohols
accomplish
rapid
access
for
novel
isochromenones
by
means
rhodium
catalysis
from
readily
available
starting
materials.
This
operationally
simple
protocol
features
broad
substrate
scope
wide
functional
group
tolerance.
Importantly,
circumvents
need
any
stoichiometric
metal
oxidants
proceeds
under
aerobic
conditions.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(30), P. 6303 - 6308
Published: May 30, 2024
Thioesterase
(TE)
domain
exerts
a
great
influence
over
the
structure
of
final
product
and
TE-released
nonreduced
polyketides
(nrPKs)
retain
aromaticity.
3-Methylene
isochromanones
are
lactones
with
unique
olefin
at
C3
that
disrupts
aromaticity,
whose
biosynthetic
details
speculative.
Our
study
unveils
complete
biosynthesis
ascochin,
in
which
construction
3-methylene
isochromanone
backbone
is
achieved
by
nonreducing
polyketide
synthase
(nrPKS)
alone
two
subsequent
oxidations
involved.
Intriguingly,
TE
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(37), P. 6830 - 6834
Published: Sept. 8, 2023
A
Ru-catalyzed
carboxylate
directed
C–H
allylation
and
iodolactonization
of
benzoic
acids
has
been
accomplished
with
Morita–Baylis–Hillman
adducts
as
the
coupling
partner
in
environmentally
benign
water
solvent.
The
redox-neutral
conditions,
use
a
solvent,
substrate
scope,
functional
group
tolerance,
mutation
natural
products
drug
molecules
are
important
practical
features.
The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(5), P. 3672 - 3676
Published: Feb. 21, 2024
The
Rh(III)-catalyzed
annulation
of
benzoic
acids
with
nitroalkenes
was
disclosed
to
afford
a
wide
range
3,4-disubstituted
isochroman-1-ones
excellent
regioselectivity
and
high
catalytic
efficiency.
Both
aromatic
aliphatic
participated
in
this
cyclization
reaction
successfully.
synthetic
value
proven
by
series
derivatizations.
Furthermore,
reliable
mechanism
is
outlined
on
the
basis
experimental
investigations
related
precedents.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(31), P. 5688 - 5692
Published: Aug. 3, 2022
A
Rh(III)-catalyzed
C–H
activation
of
α-keto
oximes
and
a
cyclization
cascade
with
diazo
compounds
were
developed
to
construct
the
highly
fused
indano[1,2-b]azirine
frameworks
in
good
yields
broad
range
substrates
under
mild
reaction
conditions.
More
intriguingly,
[4+1+1]
sequential
annulation
is
demonstrated
for
first
time
this
opened
new
mode
oximes.
These
derivatives
could
also
be
further
transformed
into
intriguing
privileged
drug
scaffolds.
European Journal of Organic Chemistry,
Journal Year:
2022,
Volume and Issue:
2022(32)
Published: July 27, 2022
Abstract
A
rhodium‐catalyzed
oxidative
cross
coupling/annulation
of
indole
carboxylic
acids
with
unsymmetric
internal
trifluoromethylated
alkynes
was
accomplished,
which
enabled
direct
access
to
diverse
indolopyranones,
by
combining
indole,
pyranone
and
trifluoromethyl,
three
valid
pharmacophores,
into
one
molecule.
Diverse
indole‐3‐carboxylic
indole‐2‐carboxylic
were
proved
be
suitable
reaction
partners.
Excellent
regioselectivity
dominated
electron
difference
alkynes.
Moderate
good
yields,
high
efficiency
atom
economy
achieved
for
a
broad
substrate
scope
functional
group
tolerance.
