Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(46), P. 15586 - 15590
Published: Nov. 5, 2018
We
disclose
unprecedented
synergistic
bimetallic
Ni/Ag
and
Ni/Cu
catalysts
for
regioselective
γ,δ-diarylation
of
unactivated
alkenes
in
simple
ketimines
with
aryl
halides
arylzinc
reagents.
The
synergy,
which
generates
cationic
Ni(II)
species
during
reaction,
promotes
migratory
insertion
transmetalation
steps
suppresses
β-H
elimination
cross-coupling,
the
major
side
reactions
that
cause
serious
problems
alkene
difunctionalization.
This
diarylation
reaction
proceeds
at
remote
locations
to
imines
afford,
after
H+
workup,
diversely
substituted
γ,δ-diaryl
ketones
are
otherwise
difficult
access
readily
existing
methods.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(48), P. 20390 - 20399
Published: Nov. 19, 2020
A
visible-light-promoted
photoredox/nickel
protocol
for
the
enantioselective
three-component
carboarylation
of
alkenes
with
tertiary
and
secondary
alkyltrifluoroborates
aryl
bromides
is
described.
This
redox-neutral
allows
facile
divergent
access
to
a
wide
array
enantioenriched
β-alkyl-α-arylated
carbonyls,
phosphonates,
sulfones
in
high
yields
excellent
enantioselectivities
from
readily
available
starting
materials.
We
also
report
modular
synthesis
flurbiprofen
analogs
piragliatin
lead
compound
demonstrate
synthetic
utility.
Experimental
computational
mechanistic
studies
were
performed
gain
insights
into
mechanism
origin
chemo-
enantioselectivity.
Chemical Science,
Journal Year:
2018,
Volume and Issue:
9(23), P. 5278 - 5283
Published: Jan. 1, 2018
A
substrate-directed
approach
to
couple
alkylzinc
nucleophiles,
alkyl
halide
electrophiles,
and
non-conjugated
alkenes
under
nickel
catalysis
is
described.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(41), P. 14653 - 14659
Published: Aug. 17, 2019
Abstract
A
highly
enantioselective
dicarbofunctionalization
of
unactivated
alkenes
was
implemented
by
a
Pd‐catalyzed
asymmetric
tandem
Heck/Suzuki
coupling
reaction.
This
reaction
represents
the
first
example
intramolecular
cyclization/cross‐coupling
olefin‐tethered
aryl
halides
with
alkyl‐,
alkenyl‐
or
arylboronic
acids,
and
provides
rapid
access
to
number
chiral
compounds,
such
as
dihydrobenzofurans,
indolines,
chromanes,
indanes
bearing
quaternary
stereocenter,
in
good
yields
excellent
enantioselectivities.
The
practicality
this
validated
modification
biologically
complex
molecules
peptides,
piperitol,
CB2
receptor
agonists,
etc.
Moreover,
synthesis
two
enantiomers
can
be
easily
realized
simple
change
order
steps
sequence.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
58(35), P. 12286 - 12290
Published: June 26, 2019
Abstract
The
potential
of
merging
photoredox
and
nickel
catalysis
to
perform
multicomponent
alkene
difunctionalizations
under
visible‐light
irradiation
is
demonstrated
here.
Secondary
tertiary
alkyl
groups,
as
well
sulfonyl
moieties
can
be
added
the
terminal
position
double
bond
with
simultaneous
arylation
internal
carbon
atom
in
a
single
step
mild
reaction
conditions.
process,
devoid
stoichiometric
additives,
benefits
from
use
bench‐stable
easy‐to‐handle
reagents,
operationally
simple,
tolerates
wide
variety
functional
groups.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(6), P. 4162 - 4184
Published: Jan. 1, 2021
This
review
provides
a
comprehensive
summary
of
recent
advances
in
nickel-catalyzed
reactions
employing
tertiary
alkyl
electrophiles
for
the
construction
quaternary
carbon
centers.
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(31), P. 9801 - 9805
Published: July 26, 2018
We
report
a
Ni-catalyzed
regioselective
alkylarylation
of
vinylarenes
with
alkyl
halides
and
arylzinc
reagents
to
generate
1,1-diarylalkanes.
The
reaction
proceeds
well
primary,
secondary
tertiary
halides,
electronically
diverse
reagents.
Mechanistic
investigations
by
radical
probes,
competition
studies
quantitative
kinetics
reveal
that
the
current
via
Ni(0)/Ni(I)/Ni(II)
catalytic
cycle
rate-limiting
direct
halogen
atom
abstraction
single
electron
transfer
Ni(0)-catalyst.
Chemical Communications,
Journal Year:
2019,
Volume and Issue:
56(4), P. 503 - 514
Published: Dec. 5, 2019
Primary
amines
are
one
of
the
most
predominant
functional
groups
found
in
organic
molecules.
These
entities
help
form
chemical
architecture
natural
products,
bioactive
molecules,
synthetic
building
blocks
and
catalysts.
Due
to
their
ubiquitous
presence,
development
strategies
for
construction
C-C
or
C-X
bonds
through
deaminative
processes
is
high
importance.
Deaminative
methods
offer
new
possibilities
on
retrosynthetic
rationale,
enable
late-stage-functionalization
complex
structures.
As
a
result
recent
photoinduced
processes,
variety
photo-mediated
protocols
employing
2,4,6-triphenyl-pyridinium
salts
-
Katritzky
Salts
as
activating
agents
have
been
recently
realized.
This
review
covers
developments
by
using
alkyl
radical
reservoirs,
with
particular
concern
applied
synthesis.
Chemical Society Reviews,
Journal Year:
2021,
Volume and Issue:
50(18), P. 10422 - 10450
Published: Jan. 1, 2021
This
review
highlights
a
decade-long
journey
of
Au-catalyzed
1,2-difunctionalization
reactions
C–C
multiple
bonds
that
have
been
realized
due
to
the
productive
integration
Au(
i
)/Au(
iii
)catalysis
with
unique
π-activation
mode
gold
complexes.
Journal of the American Chemical Society,
Journal Year:
2021,
Volume and Issue:
143(27), P. 10282 - 10291
Published: June 24, 2021
Transition-metal-catalyzed
dicarbofunctionalization
of
alkenes
involving
intramolecular
Heck
cyclization
followed
by
intermolecular
cross-coupling
has
emerged
as
a
powerful
engine
for
building
heterocycles
with
sterically
congested
quaternary
carbon
centers.
However,
only
exo-cyclization/cross-coupling
products
can
be
obtained;
endo-selective
cyclization/cross-coupling
not
been
reported
yet
and
still
poses
formidable
challenge.
We
herein
report
the
first
example
catalyst-controlled
regiodivergent
synthesis
five-
six-membered
benzo-fused
lactams
bearing
all-carbon
Using
chiral
Pyrox-
or
Phox-type
bidentate
ligand,
5-exo
cyclization/cross-couplings
proceed
favorably
to
produce
indole-2-ones
in
good
yields
excellent
regioselectivity
enantioselectivities
(up
98%
ee).
When
C6-carboxylic
acid-modified
2,2′-bipyridine
was
used
3,4-dihydroquinolin-2-ones
were
obtained
through
6-endo-selective
processes.
This
transformation
is
modular
tolerant
variety
functional
groups.
The
ligand
rather
than
substrate
structures
precisely
dictates
pattern.
Moreover,
synthetic
value
this
protocol
demonstrated
preparation
biologically
relevant
molecules
structural
scaffolds.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(23), P. 12532 - 12540
Published: May 30, 2023
An
asymmetric
three-component
carbosulfonylation
of
alkenes
is
presented
here.
The
reaction,
involving
the
simultaneous
formation
a
C-C
and
C-S
bond
across
π-system,
uses
dual
nickel/photoredox
catalytic
system
to
produce
both
β-aryl
β-alkenyl
sulfones
in
high
yields
with
excellent
levels
stereocontrol
(up
99:1
er).
This
protocol
exhibits
broad
substrate
scope
functional
group
tolerance
its
synthetic
potential
has
been
demonstrated
by
successful
applications
toward
pharmacologically
relevant
molecules.
A
array
control
experiments
supports
involvement
secondary
alkyl
radical
intermediate
generated
through
addition
sulfonyl
double
bond.
Moreover,
stoichiometric
cross-over
further
suggest
an
underlying
Ni(0)/Ni(I)/Ni(III)
pathway
operative
these
transformations.
