Handbook of CH‐Functionalization,
Год журнала:
2022,
Номер
unknown, С. 1 - 147
Опубликована: Окт. 2, 2022
Abstract
Tremendous
advances
in
transition
metal‐catalyzed
CH
functionalization
of
the
indole
scaffolds
have
been
recently
reported.
Great
efforts
devoted
to
directing
group
strategy
development
selectivity
achievement
overriding
both
inherent
reactivity
scaffold
and
activation
C2/C3H
bonds.
This
article
aims
highlight
elegant
methods
enabling
direct
arylation,
alkenylation,
alkylation,
alkynylation
along
with
introduction
heteroatoms
into
via
selective
strategies.
Organic Letters,
Год журнала:
2021,
Номер
23(11), С. 4233 - 4238
Опубликована: Май 21, 2021
Herein,
we
report
an
acid-controlled
highly
tunable
selectivity
of
Rh(III)-catalyzed
[4
+
2]
and
[3
3]
annulations
N-carboxamide
indoles
with
iodonium
ylides
lead
to
form
synthetically
important
tricyclic
tetracyclic
N-heterocycles.
Here,
ylide
serves
as
a
carbene
precursor.
The
protocol
proceeds
under
operationally
simple
conditions
provides
novel
scaffolds
such
3,4-dihydroindolo[1,2-c]quinazoline-1,6(2H,5H)-dione
1H-[1,3]oxazino[3,4-a]indol-1-one
derivatives
broad
range
functional
group
tolerance
moderate
excellent
yields.
Furthermore,
the
synthetic
utility
was
extended
for
various
chemical
transformations
easily
scaled
up
large-scale
level.
Chemical Communications,
Год журнала:
2022,
Номер
58(41), С. 6140 - 6143
Опубликована: Янв. 1, 2022
Highly
selective
and
switchable
[4+2]
annulations
of
2-arylindoles
with
iodonium
ylides
were
achieved
by
performing
solvent-controlled
Rh(III)-catalyzed
C-H
activations.
When
using
DCM
as
a
solvent,
the
functionalization
selectively
delivered
indolo[2,1-a]isoquinoline
derivatives.
In
contrast,
same
catalytic
system
polar
HFIP
solvent
predominately
provided
benzo[a]carbazole
moieties.
Organic Letters,
Год журнала:
2021,
Номер
23(12), С. 4624 - 4629
Опубликована: Июнь 9, 2021
Co(III)-catalyzed
highly
regio-
and
stereoselective
direct
C6
olefination
of
2-pyridones
with
alkynes
has
been
developed
the
assistance
chelation.
Upon
variation
reaction
conditions,
react
well
diaryl
via
a
olefination/directing
group
migration
pathway
to
give
tetrasubstituted
6-vinyl-2-pyridones,
but
C6-H
terminal
works
effectively
afford
only
C6-olefinated
2-pyridones.
A
judicious
choice
solvent
an
additive
is
crucial
for
catalysis.
The
protocols
feature
100%
atom
economy,
excellent
site
selectivity,
high
stereoselectivity,
ample
substrate
scope,
good
compatibility
functional
groups.
Synthetic
applications
are
demonstrated,
experimental
studies
density
theory
calculations
conducted
gain
mechanistic
insight
into
two
transformations.
Organic Letters,
Год журнала:
2022,
Номер
24(18), С. 3395 - 3400
Опубликована: Май 5, 2022
The
transition-metal-catalyzed
C-H
functionalization
of
sulfoxonium
ylides
with
alkynes
formally
participates
in
[4
+
2]
annulations
to
deliver
the
naphthol
scaffolds.
In
contrast,
herein
we
disclose
first
Rh(III)-catalyzed
activation,
followed
by
redox-neutral
[3
annulation
1,3-diynes,
which
delivers
alkynated
indenone
derivatives.
This
protocol
features
a
good
functional
group
tolerance,
broad
substrate
scope,
moderate
excellent
yields,
and
mild
reaction
conditions.
mechanism
was
supported
through
ESI-HRMS
characterizing
key
intermediates
catalytic
cycle.
Organic Letters,
Год журнала:
2021,
Номер
23(15), С. 5766 - 5771
Опубликована: Июль 19, 2021
Herein,
we
report
the
divergent
synthesis
of
alkynylated
imidazo[1,5-a]indoles
and
α,α-difluoromethylene
tetrasubstituted
alkenes
through
Rh(III)-catalyzed
[4
+
1]
annulation/alkyne
moiety
migration
C–H
alkenylation/DG
migration,
respectively.
This
protocol
features
tunable
product
selectivity,
excellent
chemo-,
regio-,
stereoselectivity,
broad
substrate
scope,
moderate
to
high
yields,
good
tolerance
functional
groups,
mild
redox-neutral
conditions.
ACS Catalysis,
Год журнала:
2021,
Номер
11(22), С. 13921 - 13934
Опубликована: Ноя. 2, 2021
Exploring
multistep
cascade
reactions
triggered
by
C–H
activation
are
recognized
as
appealing,
yet
challenging.
Herein,
we
disclose
a
Rh(III)-catalyzed
domino
coupling
of
N-carbamoyl
indoles
and
4-hydroxy-2-alkynoates
for
the
streamlined
assembly
highly
functionalized
furan-2(5H)-ones
in
which
carbamoyl-directing
group
(DG)
is
given
dual
role
an
auxiliary
migrating
acylating
reagent
via
cleavage
stable
C–N
bonds
at
room
temperature.
More
importantly,
obtained
furan-2(5H)-one
skeleton
could
be
further
under
air
situ
C5–H
hydroxylation
simply
switching
solvent
or
additive,
providing
fully
substituted
with
installation
alcohol-based
C5
quaternary
carbon
center.
Detailed
experimental
studies
density
functional
theory
calculations
reveal
that
Rh(III)-mediated
tandem
activation/alkyne
insertion/DG
migration/lactonization
accounts
developed
transformation
to
achieve
high
functionalities
observed
exclusive
selectivity.
The
potential
biological
application
class
potent
PPARγ
ligands
highlights
synthetic
utility
methodology.
This
protocol
endowed
several
salient
features
including
efficient
activation,
excellent
chemo-,
regio-,
stereoselectivity,
bond-forming
efficiency
(e.g.,
two
C–C
C–O
bonds),
solvent-
additive-controlled
product
selectivity,
good
functional-group
compatibility,
mild
redox-neutral
conditions.
The Journal of Organic Chemistry,
Год журнала:
2022,
Номер
87(21), С. 13757 - 13762
Опубликована: Окт. 25, 2022
Herein,
we
disclose
an
efficient
ruthenium-catalyzed
C–H
functionalization
of
2-arylbenzimidazoles/2-arylimidazoles
with
iodonium
ylides
leading
to
substituted
tetracyclic
and
pentacyclic
bridgehead
N-heterocycles,
wherein
ylide
acts
as
a
carbene
precursor.
For
the
first
time,
proceeds
through
Ru–carbenoid
intermediate.
Further,
synthetic
utility
this
protocol
was
successfully
shown
for
gram-scale
synthesis
useful
transformations.
Organic Letters,
Год журнала:
2021,
Номер
23(21), С. 8365 - 8369
Опубликована: Окт. 15, 2021
A
rhodium-catalyzed
diastereoselective
formal
[5
+
2]
annulation
of
indoles
with
cyclohexadienone-containing
1,6-enynes
has
been
established
via
indole
2,3-difunctionalization.
The
reaction,
probably
proceeding
through
tandem
C2–H
alkenylation
and
intramolecular
Friedel–Crafts
alkylation
relay,
provides
rapid
construction
indole-fused
oxepines
in
good
to
excellent
yields
a
broad
substrate
scope.
This
method
also
features
concomitant
cis-hydrobenzo[b]
oxepine
scaffolds,
core
unit
found
numerous
natural
products
important
biological
activities.
ACS Omega,
Год журнала:
2023,
Номер
8(31), С. 27894 - 27919
Опубликована: Июль 25, 2023
Polycyclic
fused
indoles
are
ubiquitous
in
natural
products
and
pharmaceuticals
due
to
their
immense
structural
diversity
biological
inference,
making
them
suitable
for
charting
broader
chemical
space.
Indole-based
polycycles
continue
be
fascinating
as
well
challenging
targets
synthetic
fabrication
because
of
characteristic
frameworks
possessing
biologically
intriguing
compounds
both
origin.
As
a
result,
an
assortment
new
processes
catalytic
routes
has
been
established
provide
unified
access
these
skeletons
very
efficient
selective
manner.
Transition-metal-catalyzed
processes,
particular
from
rhodium(III),
widely
used
endeavors
increase
molecular
complexity
efficiently.
In
recent
years,
this
resulted
significant
progress
reaching
scaffolds
with
enormous
activity
based
on
core
indole
skeletons.
Additionally,
Rh(III)-catalyzed
direct
C–H
functionalization
benzannulation
protocols
moieties
were
one
the
most
alluring
techniques
generate
indole-fused
polycyclic
molecules
This
review
sheds
light
developments
toward
synthesizing
by
cascade
annulation
methods
using
Rh(III)-[RhCp*Cl2]2-catalyzed
pathways,
which
align
comprehensive
sophisticated
field
functionalization.
Here,
we
looked
at
few
cascade-based
designs
catalyzed
Rh(III)
that
produced
elaborate
inspired
bioactivity.
The
also
strongly
emphasizes
mechanistic
insights
1–2,
2–3,
3–4-fused
systems,
focusing
routes.
With
emphasis
efficiency
product
diversity,
chosen
carbocycles
heterocycles
least
three
fused,
bridged,
or
spiro
cages
reviewed.
newly
created
synthesis
concepts
toolkits
accessing
diazepine,
indol-ones,
carbazoles,
benzo-indoles,
illustrative
privileged
techniques,
included
featured
collection.
Asian Journal of Organic Chemistry,
Год журнала:
2021,
Номер
11(1)
Опубликована: Ноя. 5, 2021
Abstract
A
cross‐coupling/annulation
reaction
of
sulfoxonium
ylides
with
iodonium
has
been
reported
by
Rh(III)‐catalyzed
C−H
functionalization
pathway
to
provide
a
direct
access
valuable
dihydrobenzo[
c
]chromen‐6‐one
derivatives.
In
this
catalytic
system,
ylide
functionality
acts
as
traceless
directing
group
(DG),
and
carbene
precursor
resulting
in
highly
selective
reaction.
The
synthetic
utility
methodology
is
demonstrated
diverse
transformations,
core
structure
Urolithin
derivatives
total
synthesis
cannabinol
natural
product.