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.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Май 6, 2024
Abstract
General,
catalytic
and
enantioselective
construction
of
chiral
α,α
-dialkyl
indoles
represents
an
important
yet
challenging
objective
to
be
developed.
Herein
we
describe
a
cobalt
catalyzed
anti-
Markovnikov
alkene
hydroalkylation
via
the
remote
stereocontrol
for
synthesis
other
N
-heterocycles.
This
asymmetric
C(sp
3
)−C(sp
)
coupling
features
high
flexibility
in
introducing
diverse
set
alkyl
groups
at
α
-position
The
utility
this
methodology
has
been
demonstrated
by
late-stage
functionalization
drug
molecules,
bioactive
natural
products
functional
materials,
identification
class
molecules
exhibiting
anti-apoptosis
activities
UVB-irradiated
HaCaT
cells.
Ligands
play
vital
role
controlling
reaction
regioselectivity.
Changing
ligand
from
bi-dentate
L6
tridentate
L12
enables
CoH-catalyzed
hydroalkylation.
Mechanistic
studies
disclose
that
involves
migratory
insertion
process
while
MHAT
process.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(24), С. 16892 - 16901
Опубликована: Июнь 6, 2024
The
development
of
a
catalytic
method
for
stereogenic
carbon
center
formation
holds
immense
significance
in
organic
synthesis.
Transition-metal-catalyzed
cross-coupling
reaction
has
been
regarded
as
straightforward
and
efficient
tool
stereoselectively
forging
C–C
bond.
Nevertheless,
the
creation
acyclic
all-carbon
quaternary-containing
vicinal
stereocenters
remains
notoriously
challenging
within
domain
chemistry
despite
their
prominence
various
bioactive
small
molecules.
Herein,
we
describe
palladium-catalyzed
asymmetric
multicomponent
trisubstituted
alkene
with
aryl
diazonium
salts
arylboronic
acids
to
realize
tertiary-quaternary
centers
high
regio-,
distereo-,
enantioselectivity.
Specifically,
precise
manipulation
stereoconfiguration
alkenes
enables
divergent
stereoselective
reaction,
thus
allowing
facile
construction
all
four
enantiomers.
Harnessing
ligand-swap
strategy
involving
chiral
bisoxazoline
an
achiral
fumarate
individually
accelerates
enantioselective
migratory
insertion
reductive
elimination
step
process,
supported
by
density
functional
theory
(DFT)
calculations,
obviating
requirement
neighboring
directing
group
internal
olefin
skeleton.
ACS Catalysis,
Год журнала:
2025,
Номер
unknown, С. 4450 - 4459
Опубликована: Фев. 28, 2025
Enantioselective
electrocatalyzed
C–H
activations
have
emerged
as
a
transformative
platform
for
the
assembly
of
value-added
chiral
organic
molecules.
Despite
recent
progress,
construction
multiple
C(sp3)-stereogenic
centers
via
C(sp3)–C(sp3)
bond
formation
has
thus
far
proven
to
be
elusive.
In
contrast,
we
herein
report
an
annulative
activation
strategy,
generating
Fsp3-rich
molecules
with
high
levels
diastereo-
and
enantioselectivity.
κ2-N,O-oxazoline
preligands
were
effectively
employed
in
enantioselective
cobalt(III)-catalyzed
reactions.
Using
DFT-derived
descriptors
regression
statistical
modeling,
performed
parametrization
study
on
modularity
preligands.
The
resulted
model
describing
ligands'
selectivity
characterized
by
key
steric,
electronic,
interaction
behaviors.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Апрель 10, 2025
Regiodivergent
hydroamin(d)ation
of
alkenes
presents
a
valuable
strategy
for
the
synthesis
diverse
amines
or
amides
from
common
set
starting
materials,
yet
achieving
controlled
regioselectivity
remains
significant
challenge.
In
this
work,
we
present
cobalt-catalyzed
regiodivergent
hydroamidation
alkenes,
enabling
enantioselective
ipso-
and
migratory
heterocyclic
alkenes.
The
ability
to
finely
tune
various
reaction
parameters
allows
seamless
switch
in
regioselectivity.
Notably,
selectivity
are
governed
by
choice
cobalt
catalyst
anions.
Mechanistic
studies
reveal
neutral
Co-H
species
mediating
ipso-hydroamidation
cationic
intermediate
promoting
hydroamidation.
This
protocol
exhibits
broad
substrate
scope,
high
functional
group
tolerance,
provides
an
efficient
pathway
synthetizing
structurally
amides.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(36)
Опубликована: Июнь 13, 2024
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
Chemical Science,
Год журнала:
2024,
Номер
15(23), С. 8888 - 8895
Опубликована: Янв. 1, 2024
A
highly
efficient
method
achieves
precise
construction
of
alkyl
chiral
centers
at
remote
C3-positions
in
five-membered
S/O-heterocycles
via
cobalt-catalyzed
asymmetric
hydroalkylation
heterocyclic
alkenes.
Heteroatomic
groups
in
alkenes
typically
direct
thermodynamically
favored
chain
walking
of
C═C
bonds
toward
themselves,
thereby
facilitating
C-H
bond
functionalization
near
the
heteroatoms.
We
present
herein
an
efficient
cobalt-catalyzed
contra-thermodynamic
remote
hydroboration
alkenylboronates
with
pinacolborane
to
synthesize
chiral
1,n-diboronates.
This
protocol
features
a
broad
substrate
scope,
high
functional
group
tolerance,
and
excellent
enantioselectivity.
Mechanistic
studies
indicate
involvement
chain-walking
process.
Gram-scale
reactions
various
product
derivatizations
further
highlight
its
practicality.
Chiral
phospholane
ligands
and
catalysts
have
been
widely
applied
in
asymmetric
catalysis
synthesis.
However,
the
construction
of
chiral
skeleton
remains
challenging
primarily
relies
on
use
auxiliaries
or
resolution.
In
this
work,
a
highly
enantioselective
diastereoselective
synthesis
P-stereogenic
oxides
has
achieved
through
cobalt-catalyzed
desymmetric
hydroalkylation
strategy.
This
method
enables
two
discrete
stereocenters
with
excellent
yields
enantiomeric
excesses.
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.
