Angewandte Chemie,
Год журнала:
2024,
Номер
136(47)
Опубликована: Авг. 12, 2024
Abstract
Herein,
we
disclose
a
simple
copper‐catalyzed
method
for
enantioselective
allylic
C(sp
3
)−H
oxidation
of
unsymmetrical
acyclic
alkenes,
specifically
1‐aryl‐2‐alkyl
alkenes.
The
C−H
substrates
are
used
in
limiting
amounts,
and
the
products
obtained
with
high
enantioselectivity,
E
/
Z
‐selectivity,
regioselectivity.
exhibits
broad
functional
group
tolerance,
‐alkene
mixtures
suitable
substrates.
transformation
is
enabled
by
light
irradiation,
which
sustains
copper
catalysis
photoinduced
oxidant
homolysis.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
unknown
Опубликована: Дек. 17, 2024
The
direct
enantioselective
functionalization
of
C(sp3)–H
bonds
in
organic
molecules
could
fundamentally
transform
the
synthesis
chiral
molecules.
In
particular,
oxidation
these
would
dramatically
change
production
methods
alcohols
and
esters,
which
are
prevalent
natural
products,
pharmaceuticals,
fine
chemicals.
Remarkable
advances
have
been
made
construction
carbon–carbon
carbon–nitrogen
through
bond
functionalization.
However,
formation
carbon–oxygen
from
remains
a
considerable
challenge.
We
herein
report
highly
oxidative
coupling
with
carboxylic
acids.
method
applies
to
allylic
propargylic
C–H
employs
various
acids
as
oxygenating
agents.
successfully
synthesized
range
esters
directly
readily
available
alkenes
alkynes,
greatly
simplifying
related
alcohols.
ACS Catalysis,
Год журнала:
2024,
Номер
15(1), С. 523 - 528
Опубликована: Дек. 20, 2024
A
catalytic
asymmetric
intermolecular
benzylic
C–H
amination
was
achieved
under
paddle-wheel
diruthenium
catalysis.
chiral
catalyst
incorporating
(S)-TPPTTL
(tetraphenylphthaloyl-(S)-tert-leucine)
ligand
exhibited
notable
enantioselectivity,
and
aminated
products
were
obtained
with
up
to
99%
ee.
Unique
chemoselectivity
of
the
also
found
for
allylbenzene
alkyl-naphthalene
substrates,
demonstrating
complementary
synthetic
utility
Ru(II)–Ru(III)
catalysts
Rh(II)
counterparts.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(14)
Опубликована: Фев. 13, 2024
Abstract
Enantioselective
C−H
amination
at
a
benzylic
methylene
is
vital
disconnection
towards
chiral
benzylamines.
Here
we
disclose
that
butyric
and
valeric
acid‐derived
tertiary
amides
can
undergo
highly
enantioselective
using
an
achiral
anionic
Rh
complex
ion‐paired
with
Cinchona
alkaloid‐derived
cation.
A
broad
scope
of
compounds
be
aminated
encompassing
numerous
arene
substitutions,
amides,
two
different
chain
lengths.
Excellent
tolerance
ortho
substituents
was
observed,
which
has
not
been
achieved
before
in
asymmetric
intermolecular
Rh.
We
speculate
the
amide
group
substrate
engages
hydrogen
bonding
interactions
directly
cation,
enabling
high
level
organisation
transition
state
for
amination.
This
contrast
our
previous
work
where
bearing
bond
donor
required.
Control
experiments
led
to
discovery
methyl
ethers
also
function
as
proficient
directing
groups
under
optimised
conditions,
potentially
acting
acceptors.
finding
promise
dramatically
expand
applicability
catalysts.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(47)
Опубликована: Авг. 12, 2024
Abstract
Herein,
we
disclose
a
simple
copper‐catalyzed
method
for
enantioselective
allylic
C(sp
3
)−H
oxidation
of
unsymmetrical
acyclic
alkenes,
specifically
1‐aryl‐2‐alkyl
alkenes.
The
C−H
substrates
are
used
in
limiting
amounts,
and
the
products
obtained
with
high
enantioselectivity,
E
/
Z
‐selectivity,
regioselectivity.
exhibits
broad
functional
group
tolerance,
‐alkene
mixtures
suitable
substrates.
transformation
is
enabled
by
light
irradiation,
which
sustains
copper
catalysis
photoinduced
oxidant
homolysis.
