Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(9), P. 1420 - 1424
Published: Feb. 27, 2023
The
iron-catalyzed
coupling
of
alkenes
and
enones
through
allylic
C(sp3)–H
functionalization
is
reported.
This
redox-neutral
process
employs
a
cyclopentadienyliron(II)
dicarbonyl
catalyst
simple
alkene
substrates
to
generate
catalytic
allyliron
intermediates
for
1,4-addition
chalcones
other
conjugated
enones.
use
2,4,6-collidine
as
the
base
combination
triisopropylsilyl
triflate
LiNTf2
Lewis
acids
was
found
facilitate
this
transformation
under
mild,
functional
group-tolerant
conditions.
Both
electronically
unactivated
well
allylbenzene
derivatives
could
be
employed
pronucleophilic
partners,
range
bearing
varied
substituents.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(18), P. 6810 - 6816
Published: April 28, 2021
Ru(II)-catalyzed
enantioselective
C-H
functionalization
involving
an
enantiodetermining
cleavage
step
remains
undeveloped.
Here
we
describe
a
activation/annulation
of
sulfoximines
with
α-carbonyl
sulfoxonium
ylides
using
novel
class
chiral
binaphthyl
monocarboxylic
acids
as
ligands,
which
can
be
easily
and
modularly
prepared
from
1,1'-binaphthyl-2,2'-dicarboxylic
acid.
A
broad
range
sulfur-stereogenic
were
in
high
yields
excellent
enantioselectivities
(up
to
99%
yield
ee)
via
desymmetrization,
kinetic
resolution,
parallel
resolution.
Furthermore,
the
resolution
products
transformed
sulfoxides
key
intermediates
for
kinase
inhibitors.
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.
Chemical Reviews,
Journal Year:
2023,
Volume and Issue:
123(16), P. 10079 - 10134
Published: Aug. 1, 2023
This
review
summarizes
the
advancements
in
rhodium-catalyzed
asymmetric
C–H
functionalization
reactions
during
last
two
decades.
Parallel
to
rapidly
developed
palladium
catalysis,
rhodium
catalysis
has
attracted
extensive
attention
because
of
its
unique
reactivity
and
selectivity
reactions.
In
recent
years,
Rh-catalyzed
have
been
significantly
many
respects,
including
catalyst
design,
reaction
development,
mechanistic
investigation,
application
synthesis
complex
functional
molecules.
presents
an
explicit
outline
catalysts
ligands,
mechanism,
scope
coupling
reagents,
applications.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(17), P. 7358 - 7426
Published: Jan. 1, 2022
Transition
metal
catalysis
has
contributed
immensely
to
C-C
bond
formation
reactions
over
the
last
few
decades,
and
alkylation
is
no
exception.
The
superiority
of
such
methodologies
traditional
evident
from
minimal
reaction
steps,
shorter
times,
atom
economy
while
also
allowing
control
regio-
stereo-selectivity.
In
particular,
hydrocarbonation
alkenes
grabbed
increased
attention
due
its
fundamental
ability
effectively
selectively
synthesise
a
wide
range
industrially
pharmaceutically
relevant
moieties.
This
review
attempts
provide
scientific
viewpoint
systematic
analysis
recent
developments
in
transition-metal-catalyzed
various
C-H
bonds
using
simple
activated
olefins.
key
features
mechanistic
studies
involved
these
transformations
are
described
briefly.
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.
Chemical Science,
Journal Year:
2021,
Volume and Issue:
12(10), P. 3726 - 3732
Published: Jan. 1, 2021
Palladium-catalyzed
asymmetric
C–H
functionalization
to
yield
axially
chiral
styrene-type
carboxylic
acids
is
described,
in
which
axial
chirality
and
sterically
hindered
group
were
incorporated
one-step.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(43), P. 23187 - 23192
Published: Aug. 26, 2021
Abstract
An
unprecedented
enantioselective
synthesis
of
spiro‐γ‐lactams
via
a
sequential
C−H
olefination/asymmetric
[4+1]
spirocyclization
under
simple
Co
II
/chiral
spiro
phosphoric
acid
(SPA)
binary
system
is
reported.
A
range
biologically
important
are
obtained
with
high
levels
enantioselectivity
(up
to
98
%
ee
).
The
concise,
asymmetric
an
aldose
reductase
inhibitor
was
successfully
achieved.
Notably,
contrast
previous
reports
that
relied
on
the
use
cyclopentadienyl
or
its
derivatives
(achiral
Cp*,
Cp
tBu
,
chiral
x
)
ligated
III
complexes
requiring
tedious
steps
prepare,
cheap
and
commercially
available
cobalt(II)
acetate
tetrahydrate
used
as
efficient
precatalyst.
ACS Catalysis,
Journal Year:
2021,
Volume and Issue:
11(7), P. 4271 - 4277
Published: March 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).
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(47)
Published: Sept. 15, 2022
Enantioselective
C-H
activation
has
surfaced
as
a
transformative
toolbox
for
the
efficient
assembly
of
chiral
molecules.
However,
despite
major
advances
in
rhodium
and
palladium
catalysis,
ruthenium(II)-catalyzed
enantioselective
thus
far
largely
proven
elusive.
In
contrast,
we
herein
report
on
highly
regio-,
diastereo-
alkylation.
The
key
to
success
was
represented
by
identification
novel
C2-symmetric
imidazolidine
carboxylic
acids
(CICAs),
which
are
easily
accessible
one-pot
fashion,
effective
ligands.
This
ruthenium/CICA
system
enabled
installation
central
axial
chirality,
featured
excellent
branched
linear
ratios
with
generally
>20
:
1
dr
up
98
2
er.
Mechanistic
studies
experiment
computation
were
carried
out
understand
catalyst
mode
action.