Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(37)
Published: June 25, 2024
Abstract
Chiral
allylic
alcohols
are
highly
prized
in
synthetic
chemistry
due
to
their
versatile
reactivity
stemming
from
both
alkenyl
and
hydroxyl
functionalities.
While
the
Nozaki–Hiyama–Kishi
(NHK)
reaction
is
a
widely
used
method
for
synthesis
of
alcohols,
it
suffers
drawbacks
such
as
use
toxic
chromium
salts,
high
amounts
metal
reductants,
poor
enantiocontrol.
To
address
these
limitations,
we
present
novel
approach
involving
metallaphotoredox‐catalyzed
asymmetric
NHK
production
chiral
alcohols.
This
marries
(pseudo)halides
with
aldehydes,
leveraging
synergistic
blend
nickel
catalyst
photocatalyst.
innovative
technique
enables
oxidative
addition
insertion
just
using
nickel,
diverging
significantly
conventional
pathway
mediated
by
salts.
The
adoption
this
methodology
holds
immense
promise
crafting
spectrum
intricate
compounds,
particularly
those
significance
pharmaceuticals.
Detailed
experimental
investigations
have
shed
light
on
metallaphotoredox
process,
further
enhancing
our
understanding
enabling
advancements.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(22), P. 15453 - 15463
Published: May 25, 2024
In
contrast
to
the
asymmetric
synthesis
of
molecules
with
a
single
stereocenter
or
1,2-adjacent
stereocenters,
simultaneous
construction
acyclic
1,3-nonadjacent
stereocenters
via
catalyst
in
an
enantioselective
and
diastereoselective
manner
remains
formidable
challenge.
Here,
we
demonstrate
diastereodivergent
through
Ni-catalyzed
reductive
cyclization/cross-coupling
alkene-tethered
aryl
bromides
α-bromoamides,
which
represents
major
remaining
stereochemical
challenge
cyclization/difunctionalization
alkenes.
Using
Ming-Phos
as
ligand,
diverse
set
oxindoles
containing
were
obtained
high
levels
enantio-
diastereoselectivity.
Mechanistic
experiments
density
functional
theory
calculations
indicate
that
magnesium
salt
plays
key
role
controlling
Furthermore,
another
complementary
stereoisomeric
products
constructed
from
same
starting
materials
using
Ph-Phox
ligand.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(20), P. 13474 - 13483
Published: Oct. 5, 2023
The
utilization
of
sulfinyl
sulfones
in
transition-metal-catalyzed
synthetic
chemistry
has
rarely
been
investigated.
Here
we
report
the
design
and
nickel-catalytic
conversion
situ-generated
redox-active
for
reductive
coupling
with
a
wide
variety
organic
halides
by
dual-role
nickel
catalyst
reductant
Zn.
Mechanistic
studies
disclose
that
key
such
reaction
is
employment
sulfones,
enabling
situ
generation
electrophilic
sulfur
reagents
through
zinc-induced
reduction
facilitated
catalyst.
This
strategy
demonstrates
good
tolerance
range
functional
groups.
Furthermore,
this
method
extends
to
meta-substituted
diaryl
sulfides,
modification
complex
bioactive
molecules
synthesis
thioether-containing
drugs.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(11), P. 3196 - 3203
Published: Jan. 1, 2024
Selective
reductive
disulfuration
of
alkyl
halides
with
di/trithiosulfonate
reagents
was
developed
through
ligand
regulation,
key
features
broad
substrate
scope,
good
tolerance
and
excellent
selectivity
to
disulfides
over
trisulfides.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
63(37)
Published: June 25, 2024
Abstract
Chiral
allylic
alcohols
are
highly
prized
in
synthetic
chemistry
due
to
their
versatile
reactivity
stemming
from
both
alkenyl
and
hydroxyl
functionalities.
While
the
Nozaki–Hiyama–Kishi
(NHK)
reaction
is
a
widely
used
method
for
synthesis
of
alcohols,
it
suffers
drawbacks
such
as
use
toxic
chromium
salts,
high
amounts
metal
reductants,
poor
enantiocontrol.
To
address
these
limitations,
we
present
novel
approach
involving
metallaphotoredox‐catalyzed
asymmetric
NHK
production
chiral
alcohols.
This
marries
(pseudo)halides
with
aldehydes,
leveraging
synergistic
blend
nickel
catalyst
photocatalyst.
innovative
technique
enables
oxidative
addition
insertion
just
using
nickel,
diverging
significantly
conventional
pathway
mediated
by
salts.
The
adoption
this
methodology
holds
immense
promise
crafting
spectrum
intricate
compounds,
particularly
those
significance
pharmaceuticals.
Detailed
experimental
investigations
have
shed
light
on
metallaphotoredox
process,
further
enhancing
our
understanding
enabling
advancements.
The Chemical Record,
Journal Year:
2024,
Volume and Issue:
unknown
Published: Sept. 17, 2024
Abstract
The
transition
metal
catalyzed
coupling
reaction
has
revolutionized
the
strategies
for
forging
carbon‐carbon
bonds.
In
contrast
to
traditional
cross‐coupling
methods
using
pre‐prepared
nucleophilic
organometallic
reagents,
reductive
reactions
C−C
bonds
formation
provide
some
advantages.
Because
both
partners
are
reduced
in
final
products
a
stoichiometric
amount
of
reductant,
this
approach
not
only
avoids
need
use
sensitive
species,
but
also
provides
an
orthogonal
and
complementary
access
classical
reaction.
Notably,
feature
readily
available
fragments,
promote
good
step
economy,
exhibit
high
functional
group
tolerance
unique
chemoselectivity,
which
have
propelled
their
increasingly
popular
organic
synthesis.
recent
years,
due
low
price,
minimal
toxicity,
environmentally
benign
character,
iron‐catalyzed
garnered
significant
attention
from
synthetic
chemists
pharmacologists,
especially
coupling.
This
review
aims
insightful
overview
advances
reactions,
illustrate
possible
mechanisms.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(1)
Published: Nov. 21, 2023
Abstract
Performing
asymmetric
cross‐coupling
reactions
between
propargylic
electrophiles
and
aryl
nucleophiles
is
a
well‐established
method
to
build
enantioenriched
benzylic
alkynes.
Here,
catalytic
enantioselective
propargyl‐aryl
two
was
achieved
for
the
first
time
in
stereoconvergent
manner.
Propargylic
chlorides
were
treated
with
iodides
as
well
heteroaryl
presence
of
chiral
nickel
complex,
manganese
metal
used
stoichiometric
reductant,
allowing
construction
propargyl
C‐aryl
bond
under
mild
conditions.
An
alternative
dual
nickel/photoredox
protocol
also
developed
this
cross‐electrophile
coupling
absence
reductant.
The
potential
utility
conversion
demonstrated
facile
stereoenriched
bioactive
molecule
derivatives
medicinal
compounds
based
on
diversity
acetylenic
chemistry.
Detailed
experimental
studies
have
revealed
key
mechanistic
features
transformation.
Chemical Science,
Journal Year:
2025,
Volume and Issue:
16(10), P. 4442 - 4449
Published: Jan. 1, 2025
Catalytic
methods
by
switching
the
least
parameters
for
regioselective
and
site-divergent
transformations
to
construct
different
architectures
from
identical
readily
available
starting
materials
are
among
most
ideal
catalytic
protocols.
However,
associated
challenge
precisely
control
both
regioselectivity
site
diversity
renders
this
strategy
appealing
yet
challenging.
Herein,
Ni-catalyzed
cross-electrophile
1,2-
1,3-arylalkylations
of
N-acyl
allylic
amines
have
been
developed.
This
reductive
three-component
protocol
enables
1,2-arylalkylation
1,3-arylalkylation
with
aryl
halides
alkyl
excellent
chemo-,
regio-
site-selectivity,
representing
first
example
controlled
migratory
difunctionalization
alkenes
under
conditions.
A
wide
range
terminal
internal
unactivated
amines,
precursors
were
tolerated,
providing
straightforward
efficient
access
diverse
C(sp3)-rich
branched
aliphatic
materials.
