Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(16), P. 10079 - 10134
Published: Aug. 1, 2023
This
review
summarizes
the
advancements
in
rhodium-catalyzed
asymmetric
C–H
functionalization
reactions
during
last
two
decades.
Parallel
to
rapidly
developed
palladium
catalysis,
rhodium
catalysis
has
attracted
extensive
attention
because
of
its
unique
reactivity
and
selectivity
reactions.
In
recent
years,
Rh-catalyzed
have
been
significantly
many
respects,
including
catalyst
design,
reaction
development,
mechanistic
investigation,
application
synthesis
complex
functional
molecules.
presents
an
explicit
outline
catalysts
ligands,
mechanism,
scope
coupling
reagents,
applications.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
61(1)
Published: Oct. 22, 2021
Axially
chiral
open-chain
olefins
represent
an
underexplored
class
of
platform.
In
this
report,
two
classes
tetrasubstituted
axially
acyclic
have
been
accessed
in
excellent
enantioselectivity
and
regioselectivity
via
C-H
activation
(hetero)arenes
assisted
by
a
migratable
directing
group
en
route
to
coupling
with
sterically
hindered
alkynes.
The
indoles
bearing
N-aminocarbonyl
afforded
C-N
acrylamides
the
assistance
racemic
zinc
carboxylate
additive.
DFT
studies
suggest
β-nitrogen
elimination-reinsertion
pathway
for
migration.
Meanwhile,
employment
N-phenoxycarboxamide
delivered
C-C
enamides
migration
oxidizing
group.
Experiments
that
both
cases
(hetero)arene
substrate
adopts
well-defined
orientation
during
activation,
which
turn
determines
disposition
alkyne
migratory
insertion.
Synthetic
applications
representative
are
demonstrated.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(14), P. 8150 - 8162
Published: April 4, 2023
Difunctionalization
of
olefins
offers
an
attractive
approach
to
access
complex
chiral
structures.
Reported
herein
is
the
design
N-protected
O-allylhydroxyamines
as
bifunctional
that
undergo
catalytic
asymmetric
1,2-carboamidation
with
three
classes
(hetero)arenes
afford
amino
alcohols
via
C-H
activation.
The
C═C
bond
in
O-allylhydroxyamine
activated
by
intramolecular
electrophilic
amidating
moiety
well
a
migrating
directing
group.
carboamidation
reaction
pattern
depends
on
nature
(hetero)arene
reagent.
Simple
achiral
reacted
give
centrally
β-amino
excellent
enantioselectivity.
employment
axially
prochiral
or
racemic
heteroarenes
afforded
both
axial
and
central
chirality
enantio-
diastereoselectivity.
In
case
heteroarenes,
coupling
follows
kinetic
resolution
s-factor
up
>600.
A
nitrene-based
mechanism
has
been
suggested
based
experimental
studies,
unique
mode
induction
diastereoselectivity
proposed.
Applications
alcohol
products
have
demonstrated.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(11), P. 6692 - 6697
Published: May 24, 2021
Reported
herein
is
the
rhodium-catalyzed
enantioselective
three-component
coupling
of
arene,
diene,
and
dioxazolone
that
occurs
via
C–H
activation
en
route
to
allyl
intermediate.
This
carboamination
reaction
affords
chiral
allylic
amines
in
1,2-selectivity,
E-selectivity,
enantioselectivity,
with
electrophilic
amination
π-allyl
species
being
both
regio-
enantio-determining.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(5), P. 3083 - 3093
Published: Feb. 21, 2022
Efficient
synthesis
of
planar
chiral
ferrocene-fused
heterocyclic
molecules
is
challenging
in
asymmetric
synthesis.
Herein,
we
report
an
enantioselective
C–H
activation/annulation
ferrocenecarboxamides
with
internal
alkynes
promoted
by
CpRh(III)
catalysis.
Trisubstituted
Cp-derived
Rh
complexes
are
found
to
be
enabling
catalysts,
which
lead
a
broad
substrate
scope
good
functional
group
compatibility.
Planar
pyridone
products
obtained
high
yields
(up
90%)
excellent
enantioselectivity
99%
ee).
Combined
experimental
and
computational
studies
support
the
proposed
reaction
mechanism.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(39), P. 18081 - 18089
Published: Sept. 26, 2022
The
copper-catalyzed
enantioselective
intermolecular
radical
1,2-carboamination
of
alkenes
with
readily
accessible
alkyl
halides
is
an
appealing
strategy
for
producing
chiral
amine
scaffolds.
challenge
arises
from
the
easily
occurring
atom
transfer
addition
between
and
issue
enantiocontrol.
We
herein
describe
a
alkene
sulfoximines
in
highly
chemo-
manner.
key
to
success
this
process
conceptual
design
counterion/highly
sterically
demanded
ligand
coeffect
promote
exchange
copper(I)
forge
C–N
bonds
radicals
copper(II)
complex.
reaction
covers
bearing
distinct
electronic
properties,
such
as
aryl-,
heteroaryl-,
carbonyl-,
aminocarbonyl-substituted
ones,
various
precursors,
including
chlorides,
bromides,
iodides,
CF3
source.
Facile
transformations
deliver
many
building
blocks
interest
organic
synthesis
related
areas.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(23), P. 14754 - 14772
Published: Nov. 18, 2022
Carboamination
of
readily
available
feedstock-like
alkenes,
alkynes,
and
allenes
has
proven
to
be
an
efficient
powerful
tool
for
the
synthesis
diverse
valuable
amine
derivatives
relevance
medicinal
chemistry,
biochemistry,
material
science.
Among
these
developed
carboamination
methodologies,
direct
use
C–H
activation
strategy
leverage
process
is
particularly
attractive
due
ubiquity
such
bonds
in
organic
molecules.
In
this
review,
we
provide
overview
development
intermolecular
across
C–C
π-bonds
initiated
by
a
redox-neutral
nonannulative
manner,
with
emphasis
on
synthetic
mechanistic
aspects.
principle,
review
summarized
reactions
key
feature
involving
initial
metalation
followed
migratory
insertion
into
terminated
electrophilic
amination
quenching,
thus,
it
ordered
sources
C-
N-based
functionalities
further
divided
π-compounds.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(42), P. 29214 - 29223
Published: Oct. 9, 2024
Macrocycles
incorporating
conformationally
defined
indoles
are
widely
found
in
bioactive
natural
products.
However,
the
catalytic
enantioselective
synthesis
of
planar-chiral
via
indolization
involving
macrocyclization
remains
elusive.
Herein,
we
present
first
rhodium(III)-catalyzed
atroposelective
macrocyclization,
which
involves
C-H
activation
aniline,
and
a
subsequent
oxidation
[3
+
2]
annulation
reaction
with
an
intramolecular
alkyne.
This
protocol
achieves
construction
indoles,
planar
chirality
control
single
step.
Importantly,
this
strategy
produces
macrocyclic
atropisomers
bearing
full-carbon
ansa
chains,
represent
challenging
targets
organic
synthesis.
Thermodynamic
experiments
revealed
that
rotational
barrier
chain-linked
atropisomer
was
lower
than
oxa-ansa
chain.
The
mechanism
elucidated
by
computational
studies,
alkyne
insertion
steps
collectively
determined
enantioselectivity.
Organic Chemistry Frontiers,
Journal Year:
2022,
Volume and Issue:
9(17), P. 4583 - 4590
Published: Jan. 1, 2022
In
this
paper,
a
coupling
partner-dependent
unsymmetrical
C–H
functionalization
of
N
-phenoxyacetamides
leading
to
the
formation
sophisticated
spirocyclic
scaffolds
is
presented.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(22), P. 13921 - 13934
Published: Nov. 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.
