Synthesis,
Год журнала:
2022,
Номер
54(21), С. 4784 - 4794
Опубликована: Март 18, 2022
Abstract
Transition
metal-catalyzed
enantioselective
C–H
functionalization
has
emerged
as
an
efficient
and
powerful
strategy
to
access
various
chiral
molecules.
Recently,
this
also
provided
a
complementary
pathway
the
construction
of
P-
S-stereogenic
compounds.
In
short
review,
we
summarize
development
applications
catalytic
systems:
Pd(II)/mono-N-protected
amino
acids
(MPAA),
Pd(0)/trivalent
phosphorus
ligands,
cyclopentadienyl-ligated
metal
catalysts
[CpxM(III)]
(M
=
Rh,
Ir),
half-sandwich
d6
Ir(III)
Ru(II)
with
carboxylic
acid
(CCA)
ligand,
Ir(I)/chiral
bidentate
boryl
cation,
for
accessing
these
compounds
via
functionalization.
1
Introduction
2
Pd(II)/Mono-N-protected
Amino
Acids
3
Pd(0)/Trivalent
Phosphorus
Chiral
Ligands
4
Cyclopentadienyl-Ligated
Metal
Catalysts
Ir)
5
Half-sandwich
Carboxylic
Acid
Ligand
6
Ir(I)/Chiral
Bidentate
Boryl
7
Cation
8
Conclusion
Outlook
ACS Catalysis,
Год журнала:
2021,
Номер
11(11), С. 6455 - 6466
Опубликована: Май 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,
Год журнала:
2022,
Номер
61(28)
Опубликована: Май 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,
Год журнала:
2021,
Номер
60(28), С. 15510 - 15516
Опубликована: Апрель 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.
Organic Letters,
Год журнала:
2020,
Номер
22(23), С. 9199 - 9202
Опубликована: Ноя. 13, 2020
Axially
chiral
atropisomeric
compounds
are
widely
applied
in
asymmetric
catalysis
and
medicinal
chemistry,
efficient
methods
for
their
synthesis
high
demand.
This
applies
particular
to
atropisomers
derived
from
five-membered
aromatic
rings
because
lower
barrier
rotation
among
the
biaryl
axis
limits
synthesis.
We
report
here
an
enantioselective
C–H
functionalization
method
using
our
RhJasCp
complex
of
atropisomer
types
that
can
be
accessed
three
different
five-membered-ring
heterocycles.
ACS Catalysis,
Год журнала:
2021,
Номер
11(15), С. 9151 - 9158
Опубликована: Июль 9, 2021
In
this
report,
distally
disposed
axial
and
central
chirality
has
been
installed
in
a
synergistic
fashion
via
rhodium-catalyzed
C–H
alkylation
of
benzamides
using
N-arylmaleimide
as
the
alkylating
reagent,
which
enantio-
diastereo-determining
steps
are
merged
into
single
one.
The
coupling
system
features
mild
reaction
conditions,
broad
substrate
scope,
excellent
diastereoselectivity.
chiral
induction
enabled
by
judicious
choice
rhodium
cyclopentadienyl
catalyst
that
serves
to
control
both
orientation
olefin
unit
prochiral
C–N
bond.
ACS Catalysis,
Год журнала:
2021,
Номер
11(7), С. 4271 - 4277
Опубликована: Март 22, 2021
Enantioselective
C(sp3)–H
functionalization
reactions
using
high-valent
group
9
metal
catalysts
with
cyclopentadienyl
ligands
have
been
achieved
by
the
introduction
of
appropriate
chiral
carboxylic
acids.
However,
diversity
acids,
as
well
that
applicable
substrate
structures
remains
limited.
Herein,
we
report
pseudo-C2-symmetric
tunable
acids
a
binaphthyl
backbone
and
their
application
to
enantioselective
amidation
2-alkylpyridines
related
heteroaromatic
substrates.
The
fixed
cyclic
structure
pseudo-C2-symmetry
developed
would
reduce
conformational
flexibility
ambiguity.
combination
an
optimal
acid
sterically
hindered
rhodium
catalyst
(Cp*tBuRhIII)
exhibited
high
enantioselectivity
(up
96:4
er).
ACS Catalysis,
Год журнала:
2022,
Номер
12(15), С. 9083 - 9091
Опубликована: Июль 14, 2022
Transition-metal-catalyzed
asymmetric
C–H
activation
reactions
generally
rely
on
the
design
of
ligands
with
sterically
bulky
groups
to
create
a
chiral
environment
for
enantioinduction
through
steric
repulsion.
Here
we
describe
an
Ir(III)-catalyzed
enabled
by
noncovalent
interactions.
A
broad
range
sulfur-stereogenic
sulfoximines
was
prepared
in
high
yields
excellent
enantioselectivities
via
activation/annulation
diazo
compounds.
Desymmetrization,
kinetic
resolution,
and
parallel
resolution
are
compatible
this
protocol.
Detailed
DFT
calculations
suggested
that
N–H···O
hydrogen
bonding
interaction
between
sulfoximine
carboxylic
acid
ligand
crucial
enantiocontrol.
Moreover,
iridacycle
intermediates
were
isolated,
characterized,
subjected
stoichiometric
reactions.
Computational
experimental
studies
cleavage
step
rate-
enantio-determining
step.
