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.
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:
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.
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
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.
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.
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.
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.
Chemical Science,
Год журнала:
2024,
Номер
15(36), С. 14865 - 14871
Опубликована: Янв. 1, 2024
A
novel
photoinduced
Co/Ni-cocatalyzed
Markovnikov
hydroarylation
of
unactivated
alkenes
with
aryl
bromides
by
using
proton
as
a
hydrogen
source
has
been
developed
for
the
first
time.
