The Journal of Organic Chemistry,
Journal Year:
2021,
Volume and Issue:
87(2), P. 1240 - 1248
Published: Dec. 29, 2021
We
present
here
a
rhodium-catalyzed
oxidative
three-point
double
annulation
of
enaminones
with
propargylic
alcohols
via
C–H
and
C–N
bond
activation
to
access
arylnaphthalene-based
lignan
derivatives.
The
key
step
in
the
reaction
is
regioselective
insertion
alcohol
into
rhoda-cycle,
result
hydroxyl
rhodium
coordination.
Necessary
control
experiments
KIE
studies
were
conducted
determine
mechanism.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(11), P. 6455 - 6466
Published: May 17, 2021
Enantioselective
C–H
functionalization
is
a
powerful
tool
for
synthesizing
chiral
molecules.
In
the
past
few
years,
combination
of
high-valent
group
9
metals
with
achiral
Cpx
ligands
and
carboxylic
acids
(CCA)
has
emerged
as
promising
catalytic
system
to
enable
selective
cleavage
enantiotopic
bonds.
This
Perspective
summarizes
background,
catalyst
design,
applied
reactions
in
detail,
followed
by
discussion
future
directions.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(28)
Published: May 2, 2022
Abstract
Among
sulfoximine
derivatives
containing
a
chiral
sulfur
center,
benzothiadiazine‐1‐oxides
are
important
for
applications
in
medicinal
chemistry.
Here,
we
report
that
the
combination
of
an
achiral
cobalt(III)
catalyst
and
pseudo‐
C
2
‐symmetric
H
8
‐binaphthyl
carboxylic
acid
enables
asymmetric
synthesis
from
sulfoximines
dioxazolones
via
enantioselective
C−H
bond
cleavage.
With
optimized
protocol,
with
several
functional
groups
can
be
accessed
high
enantioselectivity.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(15)
Published: Jan. 30, 2024
Abstract
The
combination
of
achiral
Cp*Rh(III)
with
chiral
carboxylic
acids
(CCAs)
represents
an
efficient
catalytic
system
in
transition
metal‐catalyzed
enantioselective
C−H
activation.
However,
this
hybrid
catalysis
is
limited
to
redox‐neutral
activation
reactions
and
the
adopt
oxidative
remains
elusive
pose
a
significant
challenge.
Herein,
we
describe
development
electrochemical
Cp*Rh(III)‐catalyzed
annulation
sulfoximines
alkynes
enabled
by
acid
(CCA)
operationally
friendly
undivided
cell
at
room
temperature.
A
broad
range
enantioenriched
1,2‐benzothiazines
are
obtained
high
yields
excellent
enantioselectivities
(up
99
%
yield
98
:
2
er).
practicality
method
demonstrated
scale‐up
reaction
batch
reactor
external
circulation.
crucial
intermediate
isolated,
characterized,
transformed,
providing
rational
support
for
Rh(III)/Rh(I)
electrocatalytic
cycle.
Organic & Biomolecular Chemistry,
Journal Year:
2021,
Volume and Issue:
19(7), P. 1438 - 1458
Published: Jan. 1, 2021
The
review
highlighted
diverse
annulations,
including
nitrogen,
oxygen,
sulfur
heterocycles
and
carbocylizations
via
Rh(iii)/Ir(iii)-catalyzed
C–H
functionalization/annulation
with
various
arene
carbene
precursors.
Chemistry - An Asian Journal,
Journal Year:
2021,
Volume and Issue:
16(5), P. 443 - 459
Published: Jan. 15, 2021
Metal
carbenes
play
a
pivotal
role
in
transition-metal-catalyzed
synthetic
transfer
reactions.
The
metal
carbene
is
generated
either
from
diazo
compound
through
facile
extrusion
of
N2
with
catalyst
or
situ
other
sources
like
triazoles,
pyriodotriazoles,
sulfoxonium
ylides
and
iodonium-ylide.
On
the
hand,
Co(III),
Rh(III)
&
Ir(III)-catalyzed
C-H
functionalizations
have
been
well
established
as
key
step
to
enable
construction
various
transformations.
Interestingly,
recent
years,
merging
these
two
concepts
activation
migratory
insertion
gained
much
attention,
particular
group
9
metal-catalyzed
arene
precursors
via
insertion.
In
this
review,
we
summarize
advances
direct
alkylation/alkenylation/arylation
also
discuss
intermediates
within
catalytic
cycles.
Organic Chemistry Frontiers,
Journal Year:
2021,
Volume and Issue:
8(8), P. 1764 - 1769
Published: Jan. 1, 2021
A
rhodium(iii)-catalyzed
formal
C–H
[5
+
1]
cyclization
of
2-pyrrolyl/indolylanilines
with
vinylene
carbonate
has
been
explored
towards
the
potent
assembly
diverse
4-methylpyrrolo[1,2-a]quinoxalines.
Organic Chemistry Frontiers,
Journal Year:
2022,
Volume and Issue:
9(8), P. 2256 - 2279
Published: Jan. 1, 2022
In
this
review
article,
we
summarized
recent
advances
in
the
transition
metal-catalyzed
heteroannulative
difunctionalization
of
alkenes
via
direct
C–H
activation
to
access
heterocyclic
frameworks.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
60(10), P. 5189 - 5192
Published: Nov. 26, 2020
Abstract
The
palladium‐catalyzed
[3+2]
annulation
of
aromatic
amides
with
maleimides
via
the
activation
ortho
benzylic
C−H
and
meta
bonds
is
reported.
Carboxamide
anilide
type
substrates
that
contain
a
2‐methylthiophenyl
group
both
participate
in
this
annulation,
indicating
presence
directing
key
for
success
reaction.
first
bond
at
followed
by
second
to
give
five‐membered
cyclic
products.
cleavage
these
irreversible.
Advanced Synthesis & Catalysis,
Journal Year:
2021,
Volume and Issue:
364(3), P. 512 - 517
Published: Nov. 30, 2021
Abstract
The
rhodium(III)‐catalyzed
C−H
bond
activation
and
vinylene
transfer
of
enaminones
with
carbonate
have
been
proposed
for
the
synthesis
substituted
1‐hydroxy‐2‐naphthaldehydes
in
49–84%
yields.
Several
preliminary
mechanistic
studies
hydroxyl‐directed
derivatization
reactions
were
also
performed.
This
method
offers
an
alternative
approach
1‐hydroxy‐2‐naphthaldehydes.
magnified
image
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(30), P. 11325 - 11331
Published: July 20, 2021
Photoinduced
in
situ
"oxidation"
of
half-sandwich
metal
complexes
to
"high-valent"
cationic
has
been
used
accelerate
catalytic
reactions.
Here,
we
report
the
unprecedented
photoinduced
"reduction"
[Rh(III)]
"low-valent"
anionic
[Rh(II)]
ate
complexes,
which
facilitate
ligand
exchange
with
electron-deficient
elements
(diboron).
This
strategy
was
realized
by
using
a
functionalized
cyclopentadienyl
(CpA3)
Rh(III)
catalyst
developed,
enabled
basic
group-directed
room
temperature
ortho-C–H
borylation
arenes.
