Angewandte Chemie,
Год журнала:
2023,
Номер
135(45)
Опубликована: Окт. 2, 2023
Abstract
Light
olefins
are
abundantly
manufactured
in
the
petroleum
industry
and
thus
represent
ideal
starting
materials
for
modern
chemical
synthesis.
Selective
divergent
transformations
of
feedstock
light
to
value‐added
chemicals
highly
sought‐after
but
remain
challenging.
Herein
we
report
an
exceptionally
regioselective
carbonickelation
alkenes
followed
by
situ
trapping
with
three
types
nucleophiles,
namely
a
reductant,
base,
or
Grignard
reagent.
This
protocol
enables
efficient
1,2‐hydrofunctionalization,
dicarbofunctionalization,
branched‐selective
Heck‐type
cross‐coupling
aryl
alkenyl
reagents
streamline
access
diverse
alkyl
arenes
complex
alkenes.
Harnessing
bulky
N
‐heterocyclic
carbene
ligands
acenaphthyl
backbones
nickel
catalysts
is
crucial
attain
high
reactivity
selectivity.
strategy
provides
rare,
modular,
platform
upgrading
expected
find
broad
applications
medicinal
chemistry
industrial
processes.
Journal of the American Chemical Society,
Год журнала:
2025,
Номер
unknown
Опубликована: Янв. 17, 2025
A
modular
platform
technology
for
the
synthesis
of
α-aryl
carbonyl
derivatives
via
Borono-Catellani-type
secondary
alkylation
arenes
is
presented.
This
practical
method
features
a
broad
substrate
scope
regarding
aryl
boronic
acid
catechol
esters,
alkyl
bromides,
and
diversified
terminating
reagents
(e.g.,
olefins,
alkynes,
Zn(CN)2),
mild
reaction
conditions,
good
functional-group
tolerance.
Importantly,
asymmetric
version
based
on
dynamic
kinetic
transformation
(DyKAT)
has
also
been
realized
by
introducing
1:1
diastereomeric
mixture
α-bromo
carboxamides
bearing
an
Evans
chiral
auxiliary
as
electrophiles,
constantly
excellent
diastereoselectivities
(>20:1
d.r.)
are
obtained.
Notably,
obtained
products
can
be
readily
transformed
into
enantioenriched
propionic
derivatives,
laying
solid
foundation
discovery
new
NSAIDs.
Through
mechanistic
studies
DFT
calculations,
critical
stereoretentive
oxidative
addition
step
revealed
in
this
Borono-Catellani
reaction,
origins
stereodiscrimination
DyKAT
well
explained.
Chemistry - A European Journal,
Год журнала:
2024,
Номер
30(31)
Опубликована: Апрель 3, 2024
Abstract
Saturated
heterocycles
are
important
class
of
structural
scaffolds
in
small‐molecule
drugs,
natural
products,
and
synthetic
intermediates.
Here,
we
disclosed
a
metal
free,
mild,
scalable
functionalization
saturated
using
vinylarenes
as
linchpin
approach.
Key
to
success
this
transformation
is
the
employing
simple
cheap
benzophenone
hydrogen
atom
transfer
(HAT)
catalyst.
This
operationally
robust
process
was
used
for
making
diverse
functionalized
heterocycles.
Furthermore,
aldehydes,
alkane,
alcohol
have
been
under
optimized
conditions.
The
potential
pharmaceutical
utility
procedure
has
also
demonstrated
by
late‐stage
bioactive
compounds
molecules.
Initial
mechanism
studies
control
experiments
were
performed
elucidate
reactions
Organic Letters,
Год журнала:
2024,
Номер
26(12), С. 2354 - 2358
Опубликована: Март 15, 2024
We
herein
disclose
a
novel
palladium-catalyzed
1,2-alkynylarylation
of
vinyl
arenes
using
haloalkynes
and
arylboronic
acids
as
coupling
partners.
This
reaction
is
characterized
by
broad
substrate
scope,
controllable
sequence,
excellent
chemo-
regioselectivities.
Mechanistic
investigations
suggest
that
the
initiated
regioselective
insertion
into
alkynyl-Pd(II)
species,
silver
salt
crucial
for
this
transformation,
serving
both
Lewis
acid
halide
scavenger.
protocol
provides
efficient
access
to
new
carbon
skeletons,
which
are
embedded
in
key
biologically
active
motifs.
Organic Letters,
Год журнала:
2024,
Номер
26(6), С. 1190 - 1195
Опубликована: Фев. 3, 2024
A
Ni-catalyzed
reductive
dialkylation
of
8-aminoquinoline-tethered
aliphatic
alkenes
with
two
unactivated
alkyl
electrophiles
is
disclosed
here.
Key
to
the
development
this
transformation
combination
primary
(pseudo)halides
and
secondary
iodides
that
produce
products
in
a
single
regioselective
manner.
The
reaction
exhibits
good
functional
group
compatibility,
its
synthetic
utility
was
demonstrated
by
concise
synthesis
precursors
biologically
relevant
molecules.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Авг. 12, 2024
Photoelectrochemical
(PEC)
cell
is
an
ideal
platform
for
organic
transformation
because
of
its
green
benefits
and
minimal
energy
consumption.
As
emerging
methodology,
the
reaction
types
photoelectrocatalytic
synthesis
(PECOS)
are
limited
to
simple
oxidation
C–H
activation
at
current
stage.
Metal
catalysis
construction
C(sp2)–N
bonds
has
not
been
touched
yet
in
PECOS.
We
introduce
here
a
PEC
method
that
successfully
engages
Ni
mild
production
aniline
derivatives.
Experimental
computational
investigations
elucidate
addition
photoanode-generated
amine
radical
catalyst
avoids
sluggish
nucleophilic
attack,
enabling
proceed
ultra-low
potential
(–0.4
V
vs.
Ag/AgNO3)
preventing
overoxidation
products
conventional
electrochemical
synthesis.
This
synergistic
strategy
exhibits
good
functional
group
tolerance
wide
substrate
scope
on
both
aryl
halides
amines,
by
which
some
important
natural
pharmaceutical
chemicals
have
modified.
The
stage
while
metal
remains
unexplored.
Here,
authors
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(45)
Опубликована: Окт. 2, 2023
Light
olefins
are
abundantly
manufactured
in
the
petroleum
industry
and
thus
represent
ideal
starting
materials
for
modern
chemical
synthesis.
Selective
divergent
transformations
of
feedstock
light
to
value-added
chemicals
highly
sought-after
but
remain
challenging.
Herein
we
report
an
exceptionally
regioselective
carbonickelation
alkenes
followed
by
situ
trapping
with
three
types
nucleophiles,
namely
a
reductant,
base,
or
Grignard
reagent.
This
protocol
enables
efficient
1,2-hydrofunctionalization,
dicarbofunctionalization,
branched-selective
Heck-type
cross-coupling
aryl
alkenyl
reagents
streamline
access
diverse
alkyl
arenes
complex
alkenes.
Harnessing
bulky
N-heterocyclic
carbene
ligands
acenaphthyl
backbones
nickel
catalysts
is
crucial
attain
high
reactivity
selectivity.
strategy
provides
rare,
modular,
platform
upgrading
expected
find
broad
applications
medicinal
chemistry
industrial
processes.
The Journal of Organic Chemistry,
Год журнала:
2023,
Номер
89(1), С. 281 - 290
Опубликована: Дек. 18, 2023
A
visible-light-driven
photoredox
dialkylation
of
styrenes
with
α-carbonyl
alkyl
bromides
and
pyridin-1-ium
salts
for
the
synthesis
polysubstituted
1,4-dihydropyridines
is
reported.
This
reaction
enables
formation
two
new
C(sp3)–C(sp3)
bonds
in
a
single
step
provides
strategy
that
employs
as
functionalized
alkylating
reagents
via
dearomatization
to
directly
trap
resulting
radicals
from
radical
addition
alkenes
then
terminate
alkene
dialkylation.
Organic Letters,
Год журнала:
2023,
Номер
25(51), С. 9225 - 9230
Опубликована: Дек. 19, 2023
Due
to
the
presence
of
carbon–carbon
double
bonds,
1,3-dienes
exhibit
great
reactivity.
A
protocol
for
site-selective
diarylation
terminal
is
reported
here.
The
transformation
facilitated
by
Ni
catalyst
without
need
additional
ligands,
utilizing
an
electrochemical
setup.
Preliminary
results
indicate
that
introducing
chiral
ligands
moderate
enantioselective
products
can
be
obtained.
This
method
affords
diversely
substituted
diarylated
occur
as
structural
motifs
in
various
natural
products.
The Journal of Organic Chemistry,
Год журнала:
2024,
Номер
unknown
Опубликована: Апрель 4, 2024
We
disclose
a
method
for
the
dibenzylation
of
alkenylarenes
with
benzyl
bromides
using
iron
powder.
This
reaction
generates
branched
alkyl
scaffolds
adorned
functionalized
aryl
rings
through
formation
two
new
C(sp3)–C(sp3)
bonds
at
vicinal
carbons
alkenes.
protocol
tolerates
electron-rich,
electron-neutral,
and
electron-poor
alkenylarenes.
Mechanistic
studies
suggest
benzylic
radical
intermediates
as
result
single-electron
transfer
from
iron,
which
is
intercepted
by
