Abstract
The
α
‐arylated
tetrahydrofurans,
commonly
found
in
biologically
active
molecules,
exhibit
diverse
biological
activities
and
pharmacological
effects.
functionalization
of
2,3‐dihydrofuran
offers
a
potential
route
for
the
synthesis
substituted
tetrahydrofurans.
Nevertheless,
development
earth‐abundant
metal‐catalyzed
regioselective
hydrofunctionalization
tetrahydrofurans
remains
to
be
pursued.
Herein,
we
report
cobalt‐catalyzed
hydroarylation
2,3‐dihydrofuran,
which
serves
as
first
example
cobalt
hydride‐catalyzed
alkene
hydroarylation.
This
reaction
provides
an
efficient
method
with
high
efficiency,
exclusive
‐arylation
selectivity,
remarkable
functional
group
compatibility.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Май 1, 2025
Enantioenriched,
substituted
tetrahydrofuran
skeletons
extensively
occur
in
natural
products,
bioactive
targets,
and
organic
frameworks.
The
rapid
diverse
synthesis
of
these
molecules
is
highly
desired
yet
challenging.
Herein,
we
present
a
practical
synthetic
strategy
for
asymmetric
allylic
C-H
bond
functionalization
oxyheterocyclic
alkenes
by
making
use
the
synergistic
catalysis
achiral
Pd
complex
chiral
N,N'-dioxide-Ni(II)
catalyst.
Notably,
chemodivergent
alkylated
products
hydroalkylated
was
readily
achieved
good
outcomes
via
regulation
solvents.
Furthermore,
post-transformation
functionalized
2,5-dihydrofurans
provides
an
innovative
route
to
access
skeleton
compounds
containing
multiple
stereocenters.
JACS Au,
Год журнала:
2024,
Номер
4(6), С. 2312 - 2322
Опубликована: Июнь 11, 2024
Enantioenriched
3-methylpyrrolidine,
with
its
unique
chiral
nitrogen-containing
core
skeleton,
exists
widely
in
various
functional
molecules,
including
natural
products,
bioactive
compounds,
and
pharmaceuticals.
Traditional
methods
for
synthesizing
these
valuable
methyl-substituted
heterocycles
often
involve
enzymatic
processes
or
complex
procedures
auxiliaries,
limiting
the
substrate
scope
efficiency.
Efficient
catalytic
methylation,
especially
an
enantioselective
manner,
has
been
a
long-standing
challenge
chemical
synthesis.
Herein,
we
present
novel
approach
remote
stereoselective
installation
of
methyl
group
onto
N-heterocycles,
leveraging
CoH-catalyzed
asymmetric
hydromethylation
strategy.
By
effectively
combining
commercial
cobalt
precursor
modified
bisoxazoline
(BOX)
ligand,
variety
easily
accessible
3-pyrrolines
can
be
converted
to
enantiopure
3-(isotopic
labeling)methylpyrrolidine
compounds
outstanding
enantioselectivity.
This
efficient
protocol
streamlines
two-step
synthesis
enantioenriched
which
previously
required
up
five
six
steps
under
harsh
conditions
expensive
starting
materials.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(36)
Опубликована: Июнь 13, 2024
Abstract
Isotopically
labeled
alkanes
play
a
crucial
role
in
organic
and
pharmaceutical
chemistry.
While
some
deuterated
methylating
agents
are
readily
available,
the
limited
accessibility
of
other
deuteroalkyl
reagents
has
hindered
synthesis
corresponding
products.
In
this
study,
we
introduce
nickel‐catalyzed
system
that
facilitates
various
deuterium‐labeled
through
hydrodeuteroalkylation
d2‐labeled
alkyl
TT
salts
with
unactivated
alkenes.
Diverging
from
traditional
reagents,
thianthrenium
(TT)
can
effectively
selectively
deuterium
at
α
position
chains
using
D
2
O
as
source
via
single‐step
pH‐dependent
hydrogen
isotope
exchange
(HIE).
Our
method
allows
for
high
incorporation,
offers
precise
control
over
site
insertion
within
an
chain.
This
technique
proves
to
be
invaluable
compounds,
especially
those
relevance.
Angewandte Chemie,
Год журнала:
2024,
Номер
136(47)
Опубликована: Авг. 12, 2024
Abstract
C(
sp
3
)
centers
adjacent
to
(hetero)
aryl
groups
are
widely
present
in
physiologically
active
molecules.
Metal‐hydride‐catalyzed
hydroalkylation
of
alkenes
represents
an
efficient
means
forging
)−C(
bonds,
boasting
advantages
as
a
wide
source
substrates,
mild
reaction
conditions,
and
facile
selectivity
manipulation.
Nevertheless,
the
vinylarenes
encounters
constraints
terms
substrate
scope,
necessitating
employment
activated
alkyl
halides
or
containing
chelating
groups,
remains
challenge.
In
this
context,
we
report
general
nickel‐hydride‐catalyzed
protocol
for
vinylarenes.
Remarkably,
system
enables
α‐selective
both
heteroaryl
under
extra
ligand‐free
condition,
demonstrating
excellent
coupling
efficiency
selectivity.
Furthermore,
through
incorporation
chiral
bisoxazoline
ligands,
have
achieved
regio‐
enantioselective
vinylpyrroles,
thereby
facilitating
synthesis
α‐branched
alkylated
pyrrole
derivatives.
Abstract
The
metal
hydride
catalyzed
alkene
hydroalkylation
enables
efficient
alkyl–alkyl
coupling,
yielding
structurally
diverse
chiral
organic
compounds.
However,
the
control
of
stereochemical
selectivity
in
still
heavily
relies
on
assistance
substrate
Lewis
basic
functional
groups
or
polar
heteroatom
groups.
We
have
recently
developed
a
cobalt
catalytic
system
and
established
paradigm
enantioselective
assisted
by
C–H···π
noncovalent
interactions.
This
approach
asymmetric
1,1-disubstituted
styrenes,
thereby
circumventing
limitations
imposed
1
Introduction
2
Reaction
Development
3
Synthetic
Applications
4
Mechanistic
Investigation
5
Conclusion
Future
Outlook
Organic Letters,
Год журнала:
2024,
Номер
26(43), С. 9288 - 9293
Опубликована: Окт. 21, 2024
A
highly
regioselective
cobalt-catalyzed
three-component
alkyl
arylation
of
acrylates
with
iodides
and
aryl
Grignard
reagents
has
been
established.
The
reaction
efficiently
provides
an
alternative
strategy
for
the
construction
α-aryl
esters
a
broad
substrate
scope
good
yields
under
mild
conditions.
practical
applicability
this
protocol
is
shown
by
scaled-up
further
transformations
products.
In
addition,
preliminary
mechanistic
explorations
demonstrated
that
radicals
generated
efficient
cobalt
catalysis
are
instantaneously
added
to
finally
afford
desired
Abstract
The
α
‐arylated
tetrahydrofurans,
commonly
found
in
biologically
active
molecules,
exhibit
diverse
biological
activities
and
pharmacological
effects.
functionalization
of
2,3‐dihydrofuran
offers
a
potential
route
for
the
synthesis
substituted
tetrahydrofurans.
Nevertheless,
development
earth‐abundant
metal‐catalyzed
regioselective
hydrofunctionalization
tetrahydrofurans
remains
to
be
pursued.
Herein,
we
report
cobalt‐catalyzed
hydroarylation
2,3‐dihydrofuran,
which
serves
as
first
example
cobalt
hydride‐catalyzed
alkene
hydroarylation.
This
reaction
provides
an
efficient
method
with
high
efficiency,
exclusive
‐arylation
selectivity,
remarkable
functional
group
compatibility.
