Synlett,
Год журнала:
2024,
Номер
36(02), С. 97 - 102
Опубликована: Май 28, 2024
Abstract
While
enantioselective
hydrofluorination
methods
for
activated
alkenes
represent
a
notable
advance,
the
resultant
enantiomeric
excesses
remain
largely
moderate,
indicating
necessity
enhancements
in
precision,
efficiency,
and
scope.
We
have
recently
developed
an
innovative
nickel
hydride
catalytic
system
that
enables
regio-
C–F
bond
formation
with
unactivated
alkenes.
By
utilizing
specially
designed
Bn-BOx
ligands
improved
selectivity,
our
approach
demonstrates
exceptional
efficiency
selectivity
β,γ-alkenyl
amide
substrates.
This
breakthrough
enhances
synthesis
of
organofluorine
compounds,
marking
significant
advancement
organic
synthesis.
1
Introduction
2
Reaction
Design
Hydrofluorination
3
Regio-
Enantioselective
4
Asymmetric
Amplification
5
Conclusions
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(13), С. 9375 - 9384
Опубликована: Март 21, 2024
Catalytic
formation
of
a
regio-
and
enantioselective
C–F
bond
chiral
center
from
readily
available
alkenes
is
crucial
goal,
yet
it
continues
to
pose
significant
challenges
in
organic
synthesis.
Here,
we
report
the
regioselective
bonds
facilitated
by
NiH
catalysis
coordination
directing
strategy
that
enables
precise
hydrofluorination
both
terminal
internal
alkenes.
Notably,
have
optimized
this
methodology
achieve
high
enantioselectivity
creating
aliphatic
stereogenic
centers
especially
with
β,γ-alkenyl
substrates,
using
tailored
Bn-BOx
ligand.
Another
pivotal
finding
our
research
identification
(+)-nonlinear
effect
under
conditions,
allowing
for
even
moderately
enantiomerically
enriched
ligands.
Given
role
fluorine
pharmaceuticals
synthetic
materials,
offers
essential
insights
into
centers,
paving
way
efficient
production
valuable
fluorinated
compounds.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(21), С. 14745 - 14753
Опубликована: Май 14, 2024
We
herein
describe
a
Ni-catalyzed
formal
hydroamidation
of
readily
available
α,β-unsaturated
carbonyl
compounds
to
afford
valuable
chiral
β-amino
acid
derivatives
(up
>99:1
e.r.)
using
dioxazolones
as
robust
amino
source.
A
wide
range
alkyl-substituted
olefins
conjugated
esters,
amides,
thioesters,
and
ketones
were
successfully
amidated
at
the
β-position
with
excellent
enantioselectivity
for
first
time.
Combined
experimental
computational
mechanistic
studies
supported
our
working
hypothesis
that
this
unconventional
β-amidation
unsaturated
substrates
can
be
attributed
polar-matched
migratory
olefin
insertion
an
(amido)(Cl)Ni
Organic Chemistry Frontiers,
Год журнала:
2024,
Номер
11(15), С. 4290 - 4317
Опубликована: Янв. 1, 2024
Nickel-catalyzed
hydrofunctionalization
of
π-substrates
is
a
possibly
effective
method
to
synthesize
several
value-added
molecular
architectures.
This
review
covers
the
NiH
catalyzed
reactions
alkenes,
alkynes
and
allenes.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(27), С. 18440 - 18450
Опубликована: Июль 1, 2024
Transition
metal-catalyzed
enantioselective
hydroamination
of
1,3-dienes
provides
a
direct
methodology
for
the
construction
chiral
allylamines.
So
far,
all
reported
examples
used
nucleophilic
amines
and
proceeded
with
3,4-regioselectivity.
Herein,
we
describe
first
example
nickel-catalyzed
1,4-hydroamination
using
trimethoxysilane
hydroxylamines
structurally
adaptable
aromatic
spiroketal
based
diphosphine
(SKP)
as
ligand,
affording
wide
array
α-substituted
allylamines
in
high
yields
excellent
regio-
enantioselectivities.
This
operationally
simple
protocol
demonstrated
broad
substrate
scope
functional
group
compatibility,
significantly
expanding
chemical
space
Experimental
DFT
studies
were
performed
to
elucidate
mechanism
rationalize
enantioselectivities
reaction.
An
intermolecular
coupling
between
sulfoximines
and
allyl
amines,
linked
to
the
picolinamide
directing
group,
is
developed
by
leveraging
a
nucleopalladation-guided
regioselective
hydroamination
strategy,
enabling
production
of
range
valuable
N-alkyl
in
high
yields.
The
protocol
features
operational
simplicity
broad
substrate
scope
was
also
amenable
aniline
nucleophiles.
Synthetic
utilities
were
showcased
through
scale-up
reactions
product
diversifications,
leading
biorelevant
molecules.
Abstract
N-Arylpiperazines
are
prominent
structures
found
in
natural
products
and
synthetic
chemical
entities,
including
therapeutic
agents.
In
this
work,
we
introduce
a
novel
strategy
for
the
effective
synthesis
of
distinctive
piperazine
compounds
through
post-Ugi
cyclization
under
transition-metal-free
conditions.
This
method
involves
formation
four-component
Ugi
adduct
by
combining
an
aldehyde,
isocyanide,
primary
propargylamine,
oxamic
acid.
Subsequently,
intramolecular
alkyne
hydroamination
reaction
occurs,
leading
to
derivative
carbon–nitrogen
bond
formation.
The
have
been
characterized
1H
13C
NMR
spectroscopy.
