Nature Communications,
Journal Year:
2021,
Volume and Issue:
12(1)
Published: Sept. 27, 2021
Abstract
Remote
functionalization
of
alkenes
via
chain
walking
has
generally
been
limited
to
C(sp
3
)–H
bonds
α
and
β
polar-functional
units,
while
γ
-C(sp
through
controlled
alkene
transposition
is
a
longstanding
challenge.
Herein,
we
describe
NiH-catalyzed
migratory
formal
hydroamination
alkenyl
amides
achieved
chelation-assisted
control,
whereby
various
amino
groups
are
installed
at
the
-position
aliphatic
chains.
By
tuning
olefin
isomerization
ligand
directing
group
optimization,
-selective
amination
can
be
stabilization
6-membered
nickellacycle
by
an
8-aminoquinoline
subsequent
interception
aminating
reagent.
A
range
amines
bond
unactivated
with
varying
alkyl
lengths,
enabling
late-stage
access
value-added
-aminated
products.
Moreover,
employing
picolinamide-coupled
substrates,
this
approach
further
extended
δ
amination.
The
chain-walking
mechanism
pathway
selectivity
investigated
experimental
computational
methods.
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(40), P. 12765 - 12769
Published: Sept. 23, 2018
A
mild,
chemo-
and
site-selective
catalytic
protocol
that
allows
for
incorporating
an
alkylboron
fragment
into
unactivated
olefins
is
described.
The
use
of
internal
enables
C–C
bond-formation
at
remote
sp3
C–H
sites,
constituting
a
complementary
conceptually
different
approach
to
existing
borylation
techniques
are
currently
available
centers.
Chemical Science,
Journal Year:
2017,
Volume and Issue:
9(3), P. 600 - 607
Published: Oct. 26, 2017
We
present
herein
a
nickel-catalyzed
dicarbofunctionalization
of
alkenes
using
readily
available
organoboronic
acids
and
organic
halides
in
three-component
fashion.
Journal of the American Chemical Society,
Journal Year:
2020,
Volume and Issue:
142(49), P. 20661 - 20670
Published: Nov. 24, 2020
Electrochemistry
grants
direct
access
to
reactive
intermediates
(radicals
and
ions)
in
a
controlled
fashion
toward
selective
organic
transformations.
This
feature
has
been
demonstrated
variety
of
alkene
functionalization
reactions,
most
which
proceed
via
an
anodic
oxidation
pathway.
In
this
report,
we
further
expand
the
scope
electrochemistry
reductive
alkenes.
particular,
strategic
choice
reagents
reaction
conditions
enabled
radical-polar
crossover
pathway
wherein
two
distinct
electrophiles
can
be
added
across
highly
chemo-
regioselective
fashion.
Specifically,
used
strategy
intermolecular
carboformylation,
anti-Markovnikov
hydroalkylation,
carbocarboxylation
alkenes—reactions
with
rare
precedents
literature—by
means
electroreductive
generation
alkyl
radical
carbanion
intermediates.
These
reactions
employ
readily
available
starting
materials
(alkyl
halides,
alkenes,
etc.)
simple,
transition-metal-free
display
broad
substrate
good
tolerance
functional
groups.
A
uniform
protocol
achieve
all
three
transformations
by
simply
altering
medium.
development
provides
new
avenue
for
constructing
Csp3–Csp3
bonds.
Journal of the American Chemical Society,
Journal Year:
2017,
Volume and Issue:
139(32), P. 11261 - 11270
Published: July 20, 2017
An
intermolecular
1,2-carboamination
of
unactivated
alkenes
proceeding
via
a
Pd(II)/Pd(IV)
catalytic
cycle
has
been
developed.
To
realize
this
transformation,
cleavable
bidentate
directing
group
is
used
to
control
the
regioselectivity
aminopalladation
and
stabilize
resulting
organopalladium(II)
intermediate,
such
that
oxidative
addition
carbon
electrophile
outcompetes
potential
β-hydride
elimination.
Under
optimized
reaction
conditions,
broad
range
nitrogen
nucleophiles
electrophiles
are
compatible
coupling
partners
in
reaction,
affording
moderate
high
yields.
The
products
can
be
easily
converted
free
γ-amino
acids
γ-lactams,
both
which
common
structural
motifs
found
drug
molecules
bioactive
compounds.
Reaction
kinetics
DFT
calculations
shed
light
on
mechanism
explain
empirically
observed
reactivity
trends.
Journal of the American Chemical Society,
Journal Year:
2019,
Volume and Issue:
142(1), P. 214 - 221
Published: Dec. 15, 2019
Substantial
advances
in
enantioconvergent
C(sp3)–C(sp3)
bond
formation
reactions
have
been
made
recent
years
through
the
use
of
transition-metal-catalyzed
cross-coupling
racemic
secondary
alkyl
electrophiles
with
organometallic
reagents.
Herein,
we
report
a
general
process
for
asymmetric
construction
alkyl–alkyl
bonds
adjacent
to
heteroatoms,
namely,
nickel-catalyzed
reductive
hydroalkylation
olefins
α-heteroatom
phosphorus
or
sulfur
electrophiles.
Including
readily
available
olefins,
this
reaction
has
considerable
advantages,
such
as
mild
conditions,
broad
substrate
scope,
and
good
functional
group
compatibility,
making
it
desirable
alternative
traditional
electrophile–nucleophile
reactions.
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(10), P. 3542 - 3546
Published: Feb. 23, 2018
A
Pd-catalyzed
amide-directed
enantioselective
hydrocarbofunctionalization
of
unactivated
alkenes
with
C–H
nucleophiles
has
been
developed
using
a
chiral
monodentate
oxazoline
(MOXin)
ligand.
Various
indoles
react
at
C3
position
aminoquinoline-coupled
3-alkenamides
to
give
γ
addition
products
in
good
excellent
yield
and
enantioselectivity.
This
study
represents
an
important
advance
the
development
ligands,
which
have
underexplored
for
asymmetric
catalysis.
Chemical Society Reviews,
Journal Year:
2022,
Volume and Issue:
51(17), P. 7358 - 7426
Published: Jan. 1, 2022
Transition
metal
catalysis
has
contributed
immensely
to
C-C
bond
formation
reactions
over
the
last
few
decades,
and
alkylation
is
no
exception.
The
superiority
of
such
methodologies
traditional
evident
from
minimal
reaction
steps,
shorter
times,
atom
economy
while
also
allowing
control
regio-
stereo-selectivity.
In
particular,
hydrocarbonation
alkenes
grabbed
increased
attention
due
its
fundamental
ability
effectively
selectively
synthesise
a
wide
range
industrially
pharmaceutically
relevant
moieties.
This
review
attempts
provide
scientific
viewpoint
systematic
analysis
recent
developments
in
transition-metal-catalyzed
various
C-H
bonds
using
simple
activated
olefins.
key
features
mechanistic
studies
involved
these
transformations
are
described
briefly.
Journal of the American Chemical Society,
Journal Year:
2016,
Volume and Issue:
138(46), P. 15122 - 15125
Published: Oct. 25, 2016
A
palladium(II)-catalyzed
1,2-dicarbofunctionalization
reaction
of
unactivated
alkenes
has
been
developed,
wherein
a
cleavable
bidentate
directing
group
is
used
to
control
the
regioselectivity
and
stabilize
putative
alkylpalladium(II)
intermediate.
Under
optimized
conditions,
broad
range
nucleophiles
electrophiles
were
found
participate
in
this
transformation,
providing
moderate
high
yields.
3-Butenoic
acid
derivatives
containing
internal
α-substituents
reactive
substrates,
offering
powerful
platform
for
preparing
β,γ-substituted
carbonyl
compounds
with
multiple
stereocenters.
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(17), P. 5805 - 5813
Published: April 9, 2018
A
catalytic
method
to
prepare
highly
substituted
1,3-dienes
from
two
different
alkenes
is
described
using
a
directed,
palladium(II)-mediated
C(alkenyl)–H
activation
strategy.
The
transformation
exhibits
broad
scope
across
three
synthetically
useful
substrate
classes
masked
with
suitable
bidentate
auxiliaries
(4-pentenoic
acids,
allylic
alcohols,
and
bishomoallylic
amines)
tolerates
internal
nonconjugated
alkenes,
which
have
traditionally
been
challenging
class
of
substrates
in
this
type
chemistry.
Catalytic
turnover
enabled
by
either
MnO2
as
the
stoichiometric
oxidant
or
co-catalytic
Co(OAc)2
O2
(1
atm).
Experimental
computational
studies
were
performed
elucidate
preference
for
over
other
potential
pathways.
As
part
effort,
structurally
unique
alkenylpalladium(II)
dimer
was
isolated
characterized.
