Angewandte Chemie,
Journal Year:
2020,
Volume and Issue:
132(50), P. 22895 - 22902
Published: Sept. 4, 2020
Abstract
We
report
chiral
Rh
III
cyclopentadienyl‐catalyzed
enantioselective
synthesis
of
lactams
and
isochromenes
through
oxidative
[4+1]
[5+1]
annulation,
respectively,
between
arenes
1,3‐enynes.
The
reaction
proceeds
a
C−H
activation,
alkenyl‐to‐allyl
rearrangement,
nucleophilic
cyclization
cascade.
mechanisms
the
annulations
were
elucidated
by
combination
experimental
computational
methods.
DFT
studies
indicated
that,
following
activation
alkyne
insertion,
alkenyl
intermediate
undergoes
δ
‐hydrogen
elimination
allylic
via
six‐membered
ring
transition
state
to
produce
enallene
hydride
intermediate.
Subsequent
insertion
allyl
rearrangement
affords
several
rhodium(III)
intermediates,
rare
η
4
ene‐allyl
species
with
π‐agostic
interaction
SN
2
′‐type
external
attack
nitrogen
nucleophile,
instead
C−N
reductive
elimination,
as
stereodetermining
step.
Chemical Society Reviews,
Journal Year:
2020,
Volume and Issue:
49(19), P. 7101 - 7166
Published: Jan. 1, 2020
An
important
strategy
for
the
efficient
generation
of
diversity
in
molecular
structures
is
utilization
common
starting
materials
chemodivergent
transformations.
The
most
studied
solutions
switching
chemoselectivity
rely
on
catalyst,
ligand,
additive,
solvent,
temperature,
time,
pressure,
pH
and
even
small
modifications
substrate.
In
this
review
article
several
processes
have
been
selected
such
as
inter-
intramolecular
cyclizations,
including
carba-,
oxa-,
thia-
oxazacyclizations
promoted
mainly
by
Brønsted
or
Lewis
acids,
transition
metals
organocatalysts,
well
radical
reactions.
Catalyst-controlled
intra-
intermolecular
cyclizations
are
described
to
give
five-
six-membered
rings.
Cycloaddition
reactions
involving
(2+2),
(3+2),
(3+3),
(4+1),
(4+2),
(5+2),
(6+2)
(7+2)
useful
synthesis
cyclic
systems
using
metal
catalysts
acid-controlled
processes.
Addition
carba-
heteronucleophiles
unsaturated
conjugated
substrates
can
different
adducts
via
catalyst-,
acid-
solvent-dependent
Carbonylation
amines
phenols
carried
out
ligand-controlled
metal-catalyzed
multicomponent
Ring-opening
from
cyclopropanols,
cyclopropenols
epoxides
aziridines
applied
acyclic
versus
products
under
catalyst-control
acids.
Chemodivergent
reduction
performed
dissolving
metals,
sodium
borohydride
hydrogen
transfer
conditions
solvent
control.
Oxidation
include
oxygen
control
dioxiranes,
palladium
catalyzed
cross-coupling
boronic
acids
aromatic
allenic
compounds.
Other
alkylations
allylations
catalysis,
dimerization
acetylenes,
bromination
benzylic
substrates,
A3-couplings
catalyst-
reaction
condition-dependent
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(12), P. 8407 - 8416
Published: March 14, 2024
Although
a
variety
of
chiral
porous
framework
materials
have
been
reported,
there
are
few
examples
known
to
combine
molecular
chirality,
helicity,
and
three-dimensional
(3D)
intrinsically
topology
in
one
structure,
which
is
beneficial
for
chirality
transfer
amplification.
Here,
we
report
the
synthesis
first
two
3D
covalent
organic
frameworks
(COFs)
with
an
intrinsic
Chinese Journal of Chemistry,
Journal Year:
2019,
Volume and Issue:
37(9), P. 929 - 945
Published: June 11, 2019
Generation
of
carbon‐metal
species
is
extremely
important
in
transition
metal‐catalyzed
organic
synthesis.
Among
the
various
methods,
1,4‐metal
migration
a
very
useful
way
to
create
new
species,
which
are
not
readily
accessible
via
classic
methods.
This
review
summarized
recent
advances
reactions,
involved
one
or
more
steps
migration.
It
focused
mostly
on
achievements
Pd
and
Rh‐catalyzed
along
with
some
remarkable
results
Pt,
Ir,
Co,
Fe‐involved
transformations.
Chemistry - A European Journal,
Journal Year:
2020,
Volume and Issue:
27(17), P. 5344 - 5378
Published: Oct. 30, 2020
Isoindolinone
structure
is
an
important
privileged
scaffold
found
in
a
large
variety
of
naturally
occurring
as
well
synthetic,
biologically
and
pharmaceutically
active
compounds.
Owing
to
its
crucial
role
number
applications,
the
synthetic
methodologies
for
accessing
this
heterocyclic
skeleton
have
received
significant
attention
during
past
decade.
In
general,
strategies
can
be
divided
into
two
categories:
First,
direct
utilization
phthalimides
or
phthalimidines
starting
materials
synthesis
isoindolinones;
second,
construction
lactam
and/or
aromatic
rings
by
different
catalytic
methods,
including
C-H
activation,
cross-coupling,
carbonylation,
condensation,
addition
formal
cycloaddition
reactions.
Especially
last
mentioned,
transition
metal
catalysts
provides
access
broad
range
substituted
isoindolinones.
Herein,
recent
advances
(2010-2020)
catalyzed
via
formation
new
C-C
bonds
isoindolinones
are
reviewed.
Angewandte Chemie International Edition,
Journal Year:
2020,
Volume and Issue:
59(50), P. 22706 - 22713
Published: Sept. 4, 2020
Abstract
We
report
chiral
Rh
III
cyclopentadienyl‐catalyzed
enantioselective
synthesis
of
lactams
and
isochromenes
through
oxidative
[4+1]
[5+1]
annulation,
respectively,
between
arenes
1,3‐enynes.
The
reaction
proceeds
a
C−H
activation,
alkenyl‐to‐allyl
rearrangement,
nucleophilic
cyclization
cascade.
mechanisms
the
annulations
were
elucidated
by
combination
experimental
computational
methods.
DFT
studies
indicated
that,
following
activation
alkyne
insertion,
alkenyl
intermediate
undergoes
δ
‐hydrogen
elimination
allylic
via
six‐membered
ring
transition
state
to
produce
enallene
hydride
intermediate.
Subsequent
insertion
allyl
rearrangement
affords
several
rhodium(III)
intermediates,
rare
η
4
ene‐allyl
species
with
π‐agostic
interaction
SN
2
′‐type
external
attack
nitrogen
nucleophile,
instead
C−N
reductive
elimination,
as
stereodetermining
step.
Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(16), P. 2703 - 2710
Published: June 10, 2023
Abstract
Herein,
we
develop
a
metal
catalyst‐free
protocol
for
O
‐arylation
of
benzamide
hydroxamate
esters.
The
chemoselective
‐
versus
N
the
amides
was
tuned
by
varying
electronic
and/or
steric
properties
diaryliodonium
salt
substrate.
reaction
would
preferentially
occur
sterically
and
electronically
diverse
substrates.
This
study,
which
reveals
possibility
substituent‐
reagent‐controlled
chemoselectivity,
with
salts
might
attract
interest
in
area
hypervalent
iodine
chemistry.
Catalysts,
Journal Year:
2019,
Volume and Issue:
9(10), P. 823 - 823
Published: Sept. 30, 2019
Rh(III)-catalyzed
C–H
activation
features
mild
reaction
conditions,
good
functional
group
tolerance,
high
efficiency,
and
regioselectivity.
Recently,
it
has
attracted
tremendous
attention
been
employed
to
synthesize
various
heterocycles,
such
as
indoles,
isoquinolines,
isoquinolones,
pyrroles,
pyridines,
polyheterocycles,
which
are
important
privileged
structures
in
biological
molecules,
natural
products,
agrochemicals.
In
this
short
review,
we
attempt
present
an
overview
of
recent
advances
Rh(III)-mediated
bond
generate
diverse
heterocyclic
scaffolds
with
sp3
carbon
centers.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(7), P. 1304 - 1309
Published: Feb. 8, 2024
A
Rh(III)-catalyzed
C–H
bond
activation
and
subsequent
[4+1]
annulation
of
benzamides
with
vinyl
cyclic
carbonates
have
been
developed
for
the
synthesis
isoindolinones,
in
which
electron-rich
alkenes
could
serve
as
one-carbon
units.
This
reaction
proceeds
smoothly
high
regioselectivity
under
oxidant-
silver-free
conditions
exhibits
broad
substrate
scope
functional
group
tolerance
including
some
biological
active
materials.
The
scale-up
derivatizations
product
further
demonstrate
potential
synthetic
utility
this
transformation.
