Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(49), P. 17666 - 17670
Published: Sept. 24, 2019
Abstract
C−H
bond
activation
is
mostly
limited
to
ortho
selectivity.
Activation
of
both
and
meta
bonds
constitutes
a
particularly
important
strategy
for
annulation,
but
has
rarely
been
studied
in
enantioselective
systems.
Reported
herein
rhodium(III)‐catalyzed
asymmetric
[3+2]
transannulation
arenes
with
7‐azabenzonorbornadienes.
Two
distinct
classes
have
identified
as
substrates,
the
coupling
proceeded
high
enantioselectivity
excellent
diastereoselectivity
through
sequential
bonds.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(28), P. 15510 - 15516
Published: April 16, 2021
Abstract
Chiral
cyclopentadienyl
rhodium
(CpRh)
complex‐catalyzed
asymmetric
C−H
functionalization
reactions
have
witnessed
a
significant
progress
in
organic
synthesis.
In
sharp
contrast,
the
reported
chiral
Cp
ligands
are
limited
to
C‐linked
and
often
synthetically
challenging.
To
address
these
issues,
we
developed
novel
class
of
tunable
bearing
oxygen
linkers,
which
were
efficient
catalysts
for
arylation
benzo[
h
]quinolines
with
1‐diazonaphthoquinones,
affording
axially
heterobiaryls
excellent
yields
enantioselectivity
(up
99
%
yield,
98.5:1.5
er).
Mechanistic
studies
suggest
that
reaction
is
likely
proceed
by
electrophilic
activation,
followed
coupling
cyclometalated
rhodium(III)
complex
1‐diazonaphthoquinones.
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.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(9), P. 5439 - 5446
Published: Feb. 22, 2023
Direct
construction
of
chiral
S(VI)
from
prochiral
S(II)
is
a
formidable
challenge
due
to
the
inevitable
formation
stable
S(IV).
Previous
synthetic
strategies
rely
on
conversion
S(IV)
or
enantioselective
desymmetrization
preformed
symmetrical
substrates.
Here,
we
report
desymmetrizing
hydrolysis
in
situ-generated
symmetric
aza-dichlorosulfonium
sulfenamides
for
preparation
sulfonimidoyl
chlorides,
which
could
be
used
as
general
synthon
obtaining
series
derivatives.
JACS Au,
Journal Year:
2023,
Volume and Issue:
3(3), P. 700 - 714
Published: Feb. 28, 2023
Sulfur
can
form
diverse
S(IV)
and
S(VI)
stereogenic
centers,
of
which
some
have
gained
significant
attention
recently
due
to
their
increasing
use
as
pharmacophores
in
drug
discovery
programs.
The
preparation
these
sulfur
centers
enantiopure
has
been
challenging,
progress
made
will
be
discussed
this
Perspective.
This
Perspective
summarizes
different
strategies,
with
selected
works,
for
asymmetric
synthesis
moieties,
including
diastereoselective
transformations
using
chiral
auxiliaries,
enantiospecific
compounds,
catalytic
enantioselective
synthesis.
We
discuss
the
advantages
limitations
strategies
provide
our
views
on
how
field
develop.
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.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(26), P. 8902 - 8906
Published: May 2, 2019
Abstract
Chiral
sulfoximines
with
stereogenic
sulfur
atoms
are
promising
motifs
in
drug
discovery.
We
report
an
efficient
method
to
access
chiral
through
a
C−H
functionalization
based
kinetic
resolution.
A
rhodium(III)
complex
equipped
Cp
x
ligand
selectively
participates
conjunction
phthaloyl
phenylalanine
the
activation
of
just
one
two
sulfoximine
enantiomers.
The
intermediate
reacts
various
diazo
compounds,
providing
1,2‐benzothiazines
synthetically
valuable
substitution
patterns.
Both
and
were
obtained
high
yields
excellent
enantioselectivity,
s
‐values
up
200.
utility
is
illustrated
by
synthesis
key
intermediates
pharmacologically
relevant
kinase
inhibitors.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(50), P. 18154 - 18158
Published: Oct. 8, 2019
Catalytic
enantioselective
directed
methylene
C(sp3
)-H
amidation
reactions
of
8-alkylquinolines
using
a
Cp*RhIII
/chiral
carboxylic
acid
(CCA)
hybrid
catalytic
system
are
described.
A
binaphthyl-based
chiral
efficiently
differentiates
between
the
enantiotopic
C-H
bonds,
which
leads
to
formation
C-N
bonds
with
good
enantioselectivity.
