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.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(17), P. 12053 - 12062
Published: April 16, 2024
Three-component
diene
carboaminations
offer
a
potent
means
to
access
synthetically
valuable
allylic
amines
with
rapid
molecular
complexity
escalation.
The
existing
literature
primarily
discloses
racemic
examples,
necessitating
the
use
of
halides/pseudohalides
as
substrates.
This
paper
introduces
photoinduced
Pd-catalyzed
enantioselective
three-component
carboamination
aryl-substituted
1,3-dienes,
leveraging
aliphatic
C–H
bonds
for
synthesis.
reaction
employs
10
mol
%
chiral
palladium
catalyst
and
an
excess
aryl
bromide
HAT
reagent.
approach
yields
diverse
allylamines
moderate
excellent
enantioselectivities.
Notably,
it
stands
first
instance
asymmetric
reaction,
directly
utilizing
abundant
C(sp3)–H
bearing
partners,
such
toluene-type
substrates,
ethers,
amines,
esters,
ketones.
protocol
exhibits
versatility
across
encompassing
aliphatic,
aromatic,
primary,
secondary
derivatives.
method
could
serve
versatile
platform
stereoselective
incorporation
various
nucleophiles,
dienes,
partners.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(5), P. 3725 - 3732
Published: Feb. 21, 2024
The
chiral
allylic
sulfonylated
group
is
a
unique
structural
motif
embedded
in
range
of
natural
products
and
pharmaceuticals.
Notably,
the
synthesis
structurally
diverse
derivatives
via
alkylsulfonylation
1,3-dienes
remains
underexplored
because
its
inherent
challenges
stereocontrol
regioselectivity.
Herein,
photoinduced,
palladium-catalyzed
enantioselective
1,2-alkylsulfonylation
conjugated
described.
A
wide
variety
alkyl
bromides,
1,3-dienes,
sodium
sulfinates
could
be
facilely
coupled
to
generate
value-added
with
high
enantioselectivity.
Finally,
utility
this
difunctionalization
protocol
was
demonstrated
pharmaceutical
analogue
synthesis.
Angewandte Chemie International Edition,
Journal Year:
2018,
Volume and Issue:
58(8), P. 2402 - 2406
Published: Dec. 19, 2018
The
palladium-catalyzed
Heck
reaction
is
a
well-known,
Nobel
Prize
winning
transformation
for
producing
alkenes.
Unlike
the
alkenyl
and
aryl
variants
of
reaction,
alkyl-Heck
still
underdeveloped
owing
to
competitive
side
reactions
alkyl-palladium
species.
Herein,
we
describe
development
deaminative
alkyl-Heck-type
that
proceeds
through
C-N
bond
activation
by
visible-light
photoredox
catalysis.
A
variety
aliphatic
primary
amines
were
found
be
efficient
starting
materials
this
new
process,
affording
corresponding
alkene
products
in
good
yields
under
mild
conditions.
Moreover,
strategy
was
successfully
applied
carbonylative
reactions.
Journal of the American Chemical Society,
Journal Year:
2017,
Volume and Issue:
139(42), P. 14857 - 14860
Published: Oct. 10, 2017
A
general,
efficient,
and
site-selective
visible
light-induced
Pd-catalyzed
remote
desaturation
of
aliphatic
alcohols
into
valuable
allylic,
homoallylic,
bis-homoallylic
has
been
developed.
This
transformation
operates
via
a
hybrid
Pd-radical
mechanism,
which
synergistically
combines
the
favorable
features
radical
approaches,
such
as
facile
C–H
HAT
step,
with
that
transition-metal-catalyzed
chemistry
(selective
β-hydrogen
elimination
step).
allows
achieving
superior
degrees
regioselectivity
yields
in
compared
to
those
obtained
by
state-of-the-art
methods.
The
at
unactivated
C(sp3)–H
sites
is
enabled
easily
installable/removable
Si-auxiliaries.
Formation
key
alkyl
intermediates
efficiently
induced
light
from
iodides
Pd(0)
complexes.
Notably,
this
method
requires
no
exogenous
photosensitizers
or
external
oxidants.
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.
