Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Feb. 27, 2024
Transition
metal-catalyzed
asymmetric
cyclization
of
1,6-enynes
is
a
powerful
tool
for
the
construction
chiral
nitrogen-containing
heterocycles.
Despite
notable
achievements,
these
transformations
have
been
largely
limited
to
use
aryl
or
alkenyl
metal
reagents,
and
stereoselective
stereospecific
alkylative
remains
unexploited.
Herein,
we
report
Ni-catalyzed
enantioselective
reductive
anti-arylative
with
iodides,
providing
enantioenriched
six-membered
carbo-
heterocycles
in
good
yields
excellent
enantioselectivities.
Additionally,
realized
enantiospecific
cis-alkylative
alkyl
bromides,
furnishing
five-membered
high
regioselectivity
stereochemical
fidelity.
Mechanistic
studies
reveal
that
arylative
initiated
by
oxidative
addition
Ni(0)
halides
triggered
allylic
acetates.
The
utility
this
strategy
further
demonstrated
synthesis
antiepileptic
drug
Brivaracetam.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(10), P. 6795 - 6803
Published: May 3, 2023
Herein,
we
report
a
nickel-catalyzed
asymmetric
three-component
trans-dicarbofunctionalization
of
β-substituted
α-naphthyl
propargylic
alcohols
using
readily
available
aryl
and
benzyl
halides
as
the
coupling
partners
under
reductive
conditions.
This
cross-electrophile
strategy
enables
synthesis
various
axially
chiral
allylic
bearing
tetrasubstituted
olefinic
unit
in
complete
regio-
E
selectivity,
well
high
enantiocontrol.
Relying
on
hydroxyl
group
functional
handle,
such
structural
motifs
are
successfully
derivatized
into
diverse
functional-group-rich
alkenes.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(28)
Published: May 5, 2023
The
aryl-to-vinyl
nickel
1,4-migration
(1,4-Ni
migration)
reaction
has
been
reported
for
the
first
time.
generated
alkenyl
Ni
species
undergo
a
reductive
coupling
with
unactivated
brominated
alkanes
affording
series
of
trisubstituted
olefins.
This
tandem
exhibits
mild
conditions,
broad
substrate
scope,
high
regioselectivity,
and
excellent
Z/E
stereoselectivity.
A
controlled
experiments
have
shown
that
critical
1,4-Ni
migration
process
is
reversible.
In
addition,
intermediates
obtained
after
are
highly
stereoselective
do
not
isomerization.
trace
isomerization
products
caused
by
instability
product.
Organic Letters,
Journal Year:
2023,
Volume and Issue:
25(31), P. 5756 - 5761
Published: July 28, 2023
Herein
we
report
a
nickel-catalyzed
regioselective
cross-electrophile
ring
opening
reaction
of
sulfonyl-protected
aziridines
with
trifluoromethyl-substituted
alkenes
as
the
gem-difluoroallylating
agents,
providing
new
and
efficient
entry
to
prepare
gem-difluorobishomoallylic
sulfonamides.
Moreover,
scaffold
6-fluoro-1,2,3,4-tetrahydropyridine
can
be
constructed
starting
from
products
via
NaH-mediated
intramolecular
defluorinative
nucleophilic
vinylic
substitution.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(8), P. 6228 - 6235
Published: April 10, 2024
Chiral
nickel
complexes
promoted
enantioselective
reductive
alkenylation
of
a
range
conjugated
enones,
using
alkenyl
bromides,
triflates,
and
tosylates.
The
neutral
condition
was
compatible
with
sensitive
groups
azaheteroaryl
rings.
Importantly,
in
products
can
be
readily
converted
to
functionalized
alkyl
via
iron-catalyzed
hydrofunctionalization.
Some
examples
asymmetric
N-enoyl
pyrroles
indoles
were
also
included.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: Feb. 27, 2024
Transition
metal-catalyzed
asymmetric
cyclization
of
1,6-enynes
is
a
powerful
tool
for
the
construction
chiral
nitrogen-containing
heterocycles.
Despite
notable
achievements,
these
transformations
have
been
largely
limited
to
use
aryl
or
alkenyl
metal
reagents,
and
stereoselective
stereospecific
alkylative
remains
unexploited.
Herein,
we
report
Ni-catalyzed
enantioselective
reductive
anti-arylative
with
iodides,
providing
enantioenriched
six-membered
carbo-
heterocycles
in
good
yields
excellent
enantioselectivities.
Additionally,
realized
enantiospecific
cis-alkylative
alkyl
bromides,
furnishing
five-membered
high
regioselectivity
stereochemical
fidelity.
Mechanistic
studies
reveal
that
arylative
initiated
by
oxidative
addition
Ni(0)
halides
triggered
allylic
acetates.
The
utility
this
strategy
further
demonstrated
synthesis
antiepileptic
drug
Brivaracetam.
