Science Advances,
Journal Year:
2024,
Volume and Issue:
10(48)
Published: Nov. 27, 2024
A
pair
of
enantiomers
is
known
to
have
different
biological
activities.
Two
catalysts
with
opposite
chirality
are
nearly
always
required
deliver
both
enantiomeric
products.
In
this
work,
chiral
rhodium(III)
cyclopentadienyl
complexes
repurposed
as
efficient
for
enantiodivergent
and
atroposelective
hydroamination
sterically
hindered
alkynes.
Products
been
obtained
using
the
same
or
closely
analogous
catalyst
in
good
efficiency
excellent
enantioselectivity,
enantiodivergence
was
mainly
enabled
by
an
achiral
carboxylic
acid
its
silver
salt.
Mechanistic
studies
revealed
origin
ascribable
switch
enantiodetermining
step
(alkyne
insertion
versus
protonolysis)
under
control,
which
constitutes
a
previously
unidentified
working
mode
leveraging
two
elementary
steps.
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.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(13), P. 8838 - 8844
Published: June 20, 2023
Spiro
cyclopentadienyl
rhodium
(SCpRh)
complexes
are
powerful
catalysts
for
promoting
asymmetric
C–H
functionalization
reactions.
However,
the
application
of
chiral
SCp
ligands
is
limited
due
to
tedious
synthetic
procedures
and
expensive
starting
materials.
Herein,
we
have
developed
a
series
spiro
(BCSCp)
with
6–7
steps
from
commercially
available
cheap
Bisphenol
C.
Their
corresponding
been
prepared
successfully
applied
in
enantioselective
aryl
addition
nitroalkenes,
affording
adducts
up
88%
yield
98%
ee.
Chemical Science,
Journal Year:
2023,
Volume and Issue:
14(29), P. 7999 - 8005
Published: Jan. 1, 2023
The
atroposelective
synthesis
of
axially
chiral
acyclic
olefins
remains
a
daunting
challenge
due
to
their
relatively
lower
racemization
barriers,
especially
for
trisubstituted
ones.
In
this
work,
C-H
olefination
has
been
realized
open-chain
via
activation
two
classes
(hetero)arenes
in
the
coupling
with
sterically
hindered
alkynes.
employment
phenyl
N-methoxycarbamates
as
arene
reagents
afforded
phenol-tethered
olefins,
carbamate
being
traceless
directing
group.
N-methoxy-2-indolylcarboxamides
corresponding
olefin
by
circumventing
redox-neutral
[4
+
2]
annulation.
reactions
proceeded
excellent
Z/E
selectivity,
chemoselectivity,
regioselectivity,
and
enantioselectivity
both
hydroarylation
systems.
Chemical Science,
Journal Year:
2024,
Volume and Issue:
15(33), P. 13541 - 13549
Published: Jan. 1, 2024
Herein,
we
report
an
iridium-catalyzed
asymmetric
C–H
activation
combined
with
a
desymmetrization
strategy
for
synthesizing
distal
biaxial
atropisomers
excellent
stereoselectivity,
displaying
promising
photophysical
and
chiroptical
properties.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(50), P. 10951 - 10957
Published: Dec. 10, 2024
Molecular
editing
of
quinazolinones
to
isoquinolines
by
a
novel
ruthenium-catalyzed
[4+2]
annulation
with
sulfoxonium
ylides
has
been
developed.
The
method
permits
the
precise
and
rapid
assembly
multisubstituted
aminoisoquinolines,
class
heterocycles
that
play
privileged
role
in
organic
synthesis
pharmaceutical
development.
This
new
catalytic
process
exhibits
programmability,
including
directed
C–H
acetylation,
nucleophilic
cyclization,
alcoholysis.
Remarkably,
various
2-arylquinazolinones
could
be
employed
excellent
yields
broad
functional
group
tolerance.
heterocycle-to-heterocycle
protocol
is
compatible
green
chemistry
using
an
EtOH
solvent
releasing
H2O
dimethyl
sulfoxide
as
byproducts.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: June 5, 2025
The
asymmetric
ring-opening
Suzuki-Miyaura
cross-coupling
(SMC)
reaction
of
ortho-disubstituted
aryl
bromides
with
cyclic
benzoxaboroles
has
been
developed
for
the
first
time
by
using
a
commercially
available
Et-AntPhos
as
chiral
ligand,
offering
general
access
to
diverse
axial
biaryl
benzyl
alcohols
in
high
enantioselectivity
(up
97:3
er).
This
protocol
also
features
mild
conditions
and
broad
substrate
scope,
demonstrating
potential
transformations.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(1)
Published: Nov. 16, 2023
Abstract
Axially
chiral
open‐chained
olefins
are
an
underexplored
class
of
atropisomers,
whose
enantioselective
synthesis
represents
a
daunting
challenge
due
to
their
relatively
low
racemization
barrier.
We
herein
report
rhodium(I)‐catalyzed
hydroarylative
cyclization
1,6‐diynes
with
three
distinct
classes
arenes,
enabling
highly
broad
range
axially
1,3‐dienes
that
conformationally
labile
(Δ
G
≠
(
rac
)=26.6–28.0
kcal/mol).
The
coupling
reactions
in
each
category
proceeded
excellent
enantioselectivity,
regioselectivity,
and
Z/E
selectivity
under
mild
reaction
conditions.
Computational
studies
the
quinoline
N
‐oxide
system
reveal
proceeds
via
initial
oxidative
1,6‐diyne
give
rhodacyclic
intermediate,
followed
by
σ‐bond
metathesis
between
arene
C−H
bond
Rh−C(vinyl)
bond,
subsequent
C−C
reductive
elimination
being
enantio‐determining
turnover‐limiting.
DFT‐established
mechanism
is
consistent
experimental
studies.
coupled
products
‐oxides
undergo
facile
visible
light‐induced
intramolecular
oxygen‐atom
transfer,
affording
epoxides
complete
axial‐to‐central
chirality
transfer.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(5), P. 1056 - 1061
Published: Jan. 29, 2024
The
development
of
Pd(II)-catalyzed
dearomatization
transformation
dibenzoxaborins
with
alkynes
triggered
by
transmetalation
from
boron
to
palladium
has
been
achieved,
leading
the
synthesis
spirocyclohexadienones,
an
important
skeleton
demonstrating
potential
biomedical
utility.
[3
+
2]
spiroannulation
exhibits
remarkable
regioselectivity
and
broad
substrate
scope
under
mild
reaction
conditions.
This
methodology
employs
dibenzoxaborin
as
a
establish
formal
2-phenylphenol,
which
poses
formidable
energy
barrier
destruction
aromaticity.