ACS Catalysis,
Journal Year:
2020,
Volume and Issue:
10(8), P. 4710 - 4716
Published: March 24, 2020
An
enantioselective
and
branch-regioselective
α-allylation
of
N-methyl
anilines
under
dual
palladium/photoredox
catalysis
is
described.
Readily
available
are
used
as
formal
"hard"
alkyl
nucleophiles
without
preactivation.
Acetic
acid
the
only
side
product,
which
leads
to
a
high
atom
economy
this
reaction.
This
protocol
shows
good
functional
group
tolerance
broad
scope.
A
range
chiral
homoallylic
amines
were
prepared
in
moderate
yields
(up
76%)
excellent
regioselectivities
(B:L
>
95:5
all
cases)
enantioselectivities
96%
ee)
mild
reaction
conditions.
Chemical Reviews,
Journal Year:
2021,
Volume and Issue:
121(8), P. 4373 - 4505
Published: March 19, 2021
This
Review
compiles
the
evolution,
mechanistic
understanding,
and
more
recent
advances
in
enantioselective
Pd-catalyzed
allylic
substitution
decarboxylative
oxidative
substitutions.
For
each
reaction,
catalytic
data,
as
well
examples
of
their
application
to
synthesis
complex
molecules,
are
collected.
Sections
which
we
discuss
key
aspects
for
high
selectivity
a
comparison
with
other
metals
(with
advantages
disadvantages)
also
included.
asymmetric
substitution,
data
grouped
according
type
nucleophile
employed.
Because
prominent
position
use
stabilized
carbon
nucleophiles
heteronucleophiles,
many
chiral
ligands
have
been
developed.
To
better
compare
results,
they
presented
by
ligand
types.
reactions
mainly
promoted
PHOX
or
Trost
ligands,
justifies
organizing
this
section
chronological
order.
results
used.
Journal of the American Chemical Society,
Journal Year:
2016,
Volume and Issue:
139(1), P. 2 - 14
Published: Dec. 6, 2016
In
this
Perspective
we
will
highlight
the
most
important
recent
breakthroughs
in
selective
allylboron
chemistry
(both
synthesis
and
application
of
these
species).
addition
provide
an
outlook
toward
future
promising
subfield
organic
synthesis.
Journal of the American Chemical Society,
Journal Year:
2018,
Volume and Issue:
140(49), P. 16914 - 16919
Published: Nov. 26, 2018
Highly
regio-
and
enantioselective
allylic
alkylation
has
been
achieved
enabled
by
the
merger
of
photoredox
palladium
catalysis.
In
this
dual
catalytic
process,
alkyl
radicals
generated
from
4-alkyl-1,4-dihydropyridines
act
as
coupling
partners
π-allyl
complexes.
The
generality
method
illustrated
through
reaction
a
variety
allyl
esters
with
4-alkyl-1,4-dihydropyridines.
This
mechanistically
novel
strategy
expands
scope
traditional
Pd-catalyzed
asymmetric
serves
its
alternative
potential
complement.
Organic Letters,
Journal Year:
2018,
Volume and Issue:
20(2), P. 357 - 360
Published: Jan. 5, 2018
The
efficient
Pd-catalyzed
Heck
reaction
of
diverse
tertiary
alkyl
halides
with
alkenes
has
been
developed.
Unactivated
efficiently
react
at
room
temperature
under
visible
light
irradiation
no
exogenous
photosensitizers
required.
For
activated
halides,
the
same
catalytic
system
works
well
without
light.
These
methods
offer
a
general
access
to
electronically
possessing
quaternary
and
functionalized
allylic
carbon
centers.
substituents
these
centers
include
alkyl-,
carbalkoxy-,
tosyl-,
phosphonyl-,
boronate
groups.
It
was
also
shown
that
end-game
mechanism
this
transformation
may
vary
depending
on
type
substrates
used.
Angewandte Chemie International Edition,
Journal Year:
2019,
Volume and Issue:
59(1), P. 36 - 49
Published: May 13, 2019
Abstract
Overcoming
the
inherent
difficulty
to
prepare
quaternary
carbon
stereogenic
centers,
diastereo‐
and
enantioselective
preparation
of
acyclic
backbones
possessing
vicinal
tertiary
centers
(i.e.
in
a
1,2‐relationship)
causes
distorted
geometries
represents
very
acute
problem
organic
synthesis.
Several
approaches
are
discussed
this
minireview
underlining
challenges
illustrated
by
rather
limited
number
available
practitioners.
Journal of the American Chemical Society,
Journal Year:
2017,
Volume and Issue:
139(14), P. 5027 - 5030
Published: March 25, 2017
Palladium-catalyzed
conjunctive
cross-coupling
is
used
for
the
synthesis
of
enantioenriched
allylboron
reagents.
This
reaction
employs
nonsymmetric
bis(alkenyl)borates
as
substrates
and
appears
to
occur
by
a
mechanism
that
involves
selective
activation
less
substituted
alkene
followed
migration
more
during
course
Pd-induced
metalate
rearrangement.
Journal of the American Chemical Society,
Journal Year:
2017,
Volume and Issue:
139(28), P. 9615 - 9620
Published: June 19, 2017
We
report
a
divergent
and
modular
protocol
for
the
preparation
of
acyclic
molecular
frameworks
containing
newly
created
quaternary
carbon
stereocenters.
Central
to
this
approach
is
sequence
composed
(1)
regioselective
-retentive
allyloxycarbonyl-trapped
fully
substituted
stereodefined
amide
enolates
(2)
enantioselective
palladium-catalyzed
decarboxylative
allylic
alkylation
reaction
using
novel
bisphosphine
ligand.
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(23), P. 13098 - 13104
Published: March 23, 2021
Abstract
Conventional
approaches
for
Pd‐catalyzed
ring‐opening
cross‐couplings
of
gem
‐difluorocyclopropanes
with
nucleophiles
predominantly
deliver
the
β‐fluoroalkene
scaffolds
(linear
selectivity).
Herein,
we
report
a
cooperative
strategy
that
can
completely
switch
reaction
selectivity
to
give
alkylated
α‐fluoroalkene
skeletons
(branched
The
unique
reactivity
hydrazones
enables
analogous
inner‐sphere
3,3′‐reductive
elimination
driven
by
denitrogenation,
as
well
assistance
steric‐embedded
N
‐heterocyclic
carbene
ligand,
are
key
regioselectivity.
A
wide
range
derived
from
naturally
abundant
aryl
and
alkyl
aldehydes
applicable,
various
‐difluorocyclopropanes,
including
modified
pharmaceutical
biological
molecules,
be
efficiently
functionalized
high
value
α‐fluorinated
alkene
motifs
under
mild
conditions.
