Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(20)
Published: March 19, 2024
Abstract
Herein,
multiple
types
of
chiral
Os(II)
complexes
have
been
designed
to
address
the
appealing
yet
challenging
asymmetric
C(sp
3
)−H
functionalization,
among
which
Os(II)/Salox
species
is
found
be
most
efficient
for
precise
stereocontrol
in
realizing
amidation.
As
exemplified
by
enantioenriched
pyrrolidinone
synthesis,
such
tailored
catalyst
efficiently
enables
an
intramolecular
site‐/enantioselective
amidation
γ‐position
dioxazolone
substrates,
benzyl,
propargyl
and
allyl
groups
bearing
various
substituted
forms
are
well
compatible,
affording
corresponding
γ‐lactam
products
with
good
er
values
(up
99
:
1)
diverse
functionality
(>35
examples).
The
unique
performance
advantage
developed
system
terms
catalytic
energy
profile
induction
has
further
clarified
integrated
experimental
computational
studies.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(6)
Published: Dec. 14, 2023
Abstract
Metal‐catalyzed
asymmetric
C−H
bond
annulation
strategy
offers
a
versatile
platform,
allowing
the
construction
of
complex
P‐chiral
molecules
through
atom‐
and
step‐economical
fashion.
However,
regioselective
insertion
π‐coupling
partner
between
M−C
with
high
enantio‐induction
remain
elusive.
Using
commercially
available
Co(II)
salt
chiral‐Salox
ligands,
we
demonstrate
an
unusual
protocol
for
regio‐reversal,
enantioselective
phosphinamide
bromoalkyne
desymmetrization.
The
reaction
proceeds
ligand‐assisted
enantiodetermining
cyclocobaltation
followed
by
Co−C,
subsequent
reductive
elimination,
halogen
exchange
carboxylate
resulted
in
P‐stereogenic
compounds
excellent
ee
(up
to
>99
%).
isolation
cobaltacycle
involved
catalytic
cycle
outcome
control
experiments
provide
support
plausible
mechanism.
Organic & Biomolecular Chemistry,
Journal Year:
2021,
Volume and Issue:
19(34), P. 7264 - 7275
Published: Jan. 1, 2021
In
this
review,
we
highlight
the
developments
in
chiral
Cp
x
M(
iii
)
complexes
or
achiral
complexes/chiral
carboxylic
acid-catalyzed
enantioselective
C–H
functionalization
reactions
through
migratory
insertion
of
metal–carbenes/nitrenes.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(49), P. 8906 - 8911
Published: Dec. 5, 2023
A
simple
four-step
route
to
a
chiral
tetrahydrofluorenyl
rhodium
catalyst
from
naturally
occurring
(−)-α-pinene
was
developed.
Our
approach
does
not
use
multistep
and
time-consuming
procedures
such
as
HPLC
or
diastereomeric
resolution.
The
key
success
lies
in
the
face-selective
coordination
of
sterically
hindered
ligand,
giving
only
one
complex.
This
proved
be
highly
efficient
for
asymmetric
C–H
annulation
aryl
hydroxamates
with
alkenes
(yield
up
95%,
91%
ee)
at
low
loading
(up
0.4
mol
%
based
on
Rh).
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(20)
Published: March 19, 2024
Abstract
Herein,
multiple
types
of
chiral
Os(II)
complexes
have
been
designed
to
address
the
appealing
yet
challenging
asymmetric
C(sp
3
)−H
functionalization,
among
which
Os(II)/Salox
species
is
found
be
most
efficient
for
precise
stereocontrol
in
realizing
amidation.
As
exemplified
by
enantioenriched
pyrrolidinone
synthesis,
such
tailored
catalyst
efficiently
enables
an
intramolecular
site‐/enantioselective
amidation
γ‐position
dioxazolone
substrates,
benzyl,
propargyl
and
allyl
groups
bearing
various
substituted
forms
are
well
compatible,
affording
corresponding
γ‐lactam
products
with
good
er
values
(up
99
:
1)
diverse
functionality
(>35
examples).
The
unique
performance
advantage
developed
system
terms
catalytic
energy
profile
induction
has
further
clarified
integrated
experimental
computational
studies.
