Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 23, 2025
Alcohols
and
aryl
carboxylic
acids
are
among
the
most
commercially
abundant,
synthetically
versatile,
operationally
convenient
building
blocks
in
organic
chemistry.
Despite
their
widespread
availability,
direct
formation
of
C(sp3)-C(sp2)
bonds
from
these
functional
groups
remains
a
challenge.
Recently,
our
group
developed
robust
protocols
to
harness
alcohols
as
alkyl
radical
precursors,
but
activation
relatively
unexplored.
Herein,
we
describe
merger
N-heterocyclic
carbene
(NHC)-mediated
deoxygenation
nickel-mediated
decarbonylation
toward
bond
formation.
The
utility
this
method
is
demonstrated
through
synthesis
diverse
range
aryl-alkyl
cross-coupled
products
late-stage
functionalization
complex
molecules,
including
drugs,
natural
products,
biomolecules.
Organic Letters,
Год журнала:
2024,
Номер
26(34), С. 7217 - 7221
Опубликована: Авг. 20, 2024
We
report
a
one-pot
synthesis
of
(E)-trisubstituted
enones
from
acrylic
acids
through
the
in
situ
generation
2-pyridyl
ester
and
subsequent
cross-electrophile
coupling
with
nickel
catalyst
under
reducing
conditions.
The
scope
trisubstituted
is
broad
compatible
functionality
that
can
be
challenging
established
olefination
techniques.
highlight
conditions
necessary
to
suppress
undesired
side
reactions
α,β-unsaturated
carbonyl
improve
approaches
prepare
enones.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 18, 2025
Cereblon
E3
ligase
modulatory
drugs
(CELMoDs)
can
be
used
to
target
proteins
and
mark
them
for
proteasomal
degradation
by
recruiting
cereblon
(CRBN),
the
substrate
receptor
of
CRL4CRBN
ubiquitin
complex.
Modifications
stereochemistry
regiochemistry
distal
functionality
on
CELMoDs
have
been
shown
large
effects
activity
selectivity;
however,
methods
allowing
rapid
selective
introduction
enantioenriched
moieties
are
rare.
Herein,
we
report
that
classical
CRBN-binding
glutarimide
cores
successfully
derivatized
aryl
diazoacetates.
These
diazo
derivatives,
when
in
presence
a
dirhodium
catalyst,
undergo
high-yielding
highly
enantioselective
C–H
functionalization
hydrocarbons
cyclopropanation
styrene.
products
create
not
only
molecular
glue
degrader-like
compounds
but
also
intermediates
elaborated
into
effective
bifunctional
ligand-directed
degraders.
Our
findings
highlight
both
effectiveness
catalysis
drug
discovery
context
new
method
preparing
diverse
stereoenriched
glutarimide-containing
compounds.
The Journal of Organic Chemistry,
Год журнала:
2025,
Номер
unknown
Опубликована: Март 31, 2025
Nickel-catalyzed
arylation
of
carboxylic
acids
provides
a
ligand-controlled
chemoselectivity-switchable
method
for
the
construction
C(sp2)-C(sp3)
bonds.
Here,
we
employed
density
functional
theory
to
provide
detailed
understanding
mechanism
and
origin
nickel-catalyzed
carbonyl
transformation.
This
reaction
generates
decarbonylation
products
through
oxidative
addition,
activation
C-C
bonds,
decarbonylation,
binding
alkyl
radicals
with
Ni(III)
complexes,
final
reduction
elimination
step.
The
bonds
in
aromatic
carboxylate
esters
is
more
favorable
than
C-O
bond
because
interaction
between
nickel
catalyst
π
orbitals
substrate's
moiety
during
activation.
induction
effect
ligand
group
together
determines
transfer
tendency
group.
Herein,
we
report
the
development
of
a
general
ring
expansion
strategy
that
involves
formal
self-dimerization
benzocyclobutenones
(BCBs)
through
nickel
catalysis.
These
self-dimerizations
BCBs
are
efficient
and
scalable
provide
facile
unique
construction
diverse
seven-membered
ketones
1H-isochromen-1-ones
with
high
structural
diversity.
Moreover,
solvent
effects
CO
atmosphere
play
crucial
role
in
promoting
exclusion,
which
may
address
regioselectivity
control
toward
(4
+
4
-
1)
product,
while
NaOAc
as
an
additive
under
N2
promoted
2)
product
formation.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 23, 2025
Alcohols
and
aryl
carboxylic
acids
are
among
the
most
commercially
abundant,
synthetically
versatile,
operationally
convenient
building
blocks
in
organic
chemistry.
Despite
their
widespread
availability,
direct
formation
of
C(sp3)-C(sp2)
bonds
from
these
functional
groups
remains
a
challenge.
Recently,
our
group
developed
robust
protocols
to
harness
alcohols
as
alkyl
radical
precursors,
but
activation
relatively
unexplored.
Herein,
we
describe
merger
N-heterocyclic
carbene
(NHC)-mediated
deoxygenation
nickel-mediated
decarbonylation
toward
bond
formation.
The
utility
this
method
is
demonstrated
through
synthesis
diverse
range
aryl-alkyl
cross-coupled
products
late-stage
functionalization
complex
molecules,
including
drugs,
natural
products,
biomolecules.
