Chemical Communications,
Journal Year:
2022,
Volume and Issue:
58(42), P. 6200 - 6203
Published: Jan. 1, 2022
Highly
enantioselective
palladium-catalyzed
dearomative
reductive
Heck
reaction
and
domino
Heck-Suzuki
of
2-CF3-indoles
have
been
developed.
Using
Pd(OAc)2/(R)-Synphos
as
the
catalyst
Et3SiH
a
hydride
source,
variety
indolines
bearing
2-trifluoromethyl
quaternary
stereocenter
were
obtained
via
reaction.
Alternatively,
using
Pd(dba)2/phosphoramidite
Ar4BNa
coupling
partner,
structurally
diverse
containing
two
vicinal
carbon
stereocenters
afforded
through
Angewandte Chemie International Edition,
Journal Year:
2021,
Volume and Issue:
60(37), P. 20231 - 20236
Published: July 9, 2021
An
enantioselective
consecutive
cyclization/coupling
process,
catalyzed
by
palladium
is
reported.
Stereoinduction
arises
from
an
carbopalladation,
generating
intermediate
which
promotes
a
nucleopalladation
step.
The
dual
cyclization
sequence
was
compatible
with
variety
of
alkyne-tethered
oxygen-
and
nitrogen-centered
nucleophiles,
alkenyl-tethered
aryl
iodides,
to
forge
numerous
bisheterocycles
in
good
yields
high
regio-
enantioselectivities.
Chemical Society Reviews,
Journal Year:
2023,
Volume and Issue:
53(2), P. 883 - 971
Published: Dec. 18, 2023
This
review
aims
to
collect
advancements
in
enantioselective
palladium-catalyzed
cyclization
reactions
over
the
past
eleven
years,
and
it
is
organized
into
thirteen
sections
depending
on
different
types
of
transformations
involved.
Organic Letters,
Journal Year:
2020,
Volume and Issue:
22(7), P. 2724 - 2729
Published: March 23, 2020
Herein,
we
report
a
nickel-catalyzed
asymmetric
two-component
reductive
dicarbofunctionalization
of
aryl
iodide-tethered
unactivated
alkenes
using
benzyl
chlorides
as
the
challenging
coupling
partner.
This
arylbenzylation
reaction
enables
efficient
synthesis
diverse
benzene-fused
cyclic
compounds
bearing
quaternary
stereocenter
with
high
tolerance
sensitive
functionalities
in
highly
enantioselective
manner.
The
preliminary
mechanistic
investigations
suggest
radical
chain
mechanism.
Nature Communications,
Journal Year:
2020,
Volume and Issue:
11(1)
Published: Sept. 1, 2020
Dearomative
functionalization
reactions
represent
an
important
strategy
for
the
synthesis
of
valuable
three-dimensional
molecules
from
simple
planar
aromatics.
Naphthalene
is
a
challenging
arene
towards
transition-metal-catalyzed
dearomative
difunctionalization
reactions.
Reported
herein
application
naphthalene
as
masked
conjugated
diene
in
palladium-catalyzed
1,4-diarylation
or
1,4-vinylarylation
reaction
via
tandem
Heck/Suzuki
sequence.
Three
types
1,4-dihydronaphthalene-based
spirocyclic
compounds
are
achieved
excellent
regio-
and
diastereoselectivities.
Key
to
this
transformation
inhibition
few
competitive
side
reactions,
including
intramolecular
naphthalenyl
C-H
arylation,
intermolecular
Suzuki
cross-coupling,
1,2-difunctionalization,
reductive-Heck
reaction.
Density
functional
theory
(DFT)
calculations
imply
that
facile
exergonic
insertion
double
bond
disrupts
sequence
direct
coupling,
leading
coupling
The
observed
regioselectivity
1,4-difunctionalization
due
steric
repulsions
between
introduced
aryl
group
spiro-scaffold
1,2-difunctionalization.
Organic & Biomolecular Chemistry,
Journal Year:
2021,
Volume and Issue:
19(26), P. 5673 - 5701
Published: Jan. 1, 2021
Intramolecular
carbometallation-initiated
asymmetric
transformations
are
a
general
and
powerful
approach
for
the
construction
of
carbo-
heterocyclic
systems
with
one
more
stereocenters.
In
addition,
newly
developed
multiple
cascade
reactions
an
attractive
strategy
increasing
molecular
complexity
in
step.
recent
years,
great
progress
has
been
made
this
area
use
various
palladium
nickel
complexes
P-
N-donor
chiral
ligands.
This
review
highlights
developments
intramolecular
Heck
reactions,
reductive
types
(intramolecular
Heck/Heck,
Heck/nucleophilic
trapping,
Heck/Tsuji-Trost,
Heck/Suzuki-Miyaura,
Heck/Sonogashira,
Heck/carbonylation)
synthesis
complex
molecules
over
past
5
years.
A
number
examples
from
before
2016
included
as
background
information.
Particular
attention
is
paid
to
inexpensive
highly
efficient
catalysts
considered
here.
perspective
on
current
challenges
potential
future
field
type
cyclizations
also
provided.
Chemical Science,
Journal Year:
2021,
Volume and Issue:
12(19), P. 6712 - 6718
Published: Jan. 1, 2021
A
nickel-catalyzed
reductive
asymmetric
aryl-allylation
of
tethered
unactivated
alkenes
has
been
developed,
providing
diverse
benzene-annulated
cyclic
compounds
bearing
a
quaternary
stereocenter
with
high
regio-,
E/Z-
and
enantio-selectivity.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(40)
Published: June 27, 2022
Catalysis
by
excited-state
palladium
has
emerged
as
an
active
area
of
research,
but
controlling
the
enantioselectivity
remains
a
challenge.
Herein,
we
report
use
synergistic
Pd/Cu
catalysis
to
accomplish
first
three-component
photochemical
1,4-bisalkylation
reactions
1,3-butadiene.
Consequently,
α-amino
acid
esters
bearing
quaternary
stereocenters
were
expeditiously
synthesized
from
three
simple
starting
materials:
alkyl
bromide,
butadiene,
and
aldimine
ester.
Experimental
computational
investigation
reaction
mechanism
confirmed
radical
pathway
involving
species.
The
stereochemistry
is
mainly
controlled
chiral
Cu
catalyst.
Chinese Journal of Chemistry,
Journal Year:
2022,
Volume and Issue:
41(9), P. 1099 - 1118
Published: Dec. 13, 2022
Comprehensive
Summary
Sonogashira
cross‐coupling
protocol,
typically
showing
the
reaction
between
aryl/vinyl
halide
and
terminal
alkyne,
has
been
a
widely
used
protocol
for
constructing
C(sp
2
)‐C(sp)
bond.
The
resulting
internal
alkynes
are
highly
versatile
reaching
differently
functionalized
alkyne‐containing
scaffolds
or
serving
as
valuable
synthetic
synthons
to
many
other
functional
groups.
It
is
worth
noting
that
products
originated
from
this
coupling
mostly
applicable
be
transformed
into
corresponding
Z
‐alkene,
alkane,
heterocyclic
moieties
in
natural
product
syntheses.
conditions
catalyst
systems
able
tweaked
order
facilitate
activation
of
steric
hindered
and/or
electron‐rich
electrophiles.
Pd‐catalyzed
copper‐free
caught
increasing
attention
improved
method
can
more
environmentally
friendly.
What
more,
readily
amended
allow
fusion
carbonylation
decarboxylation
step
catalytic
cycle,
thus
complex
yet
convergent
synthesis
proceed
an
operationally
simple
one‐pot
manner.
Journal of the American Chemical Society,
Journal Year:
2024,
Volume and Issue:
146(7), P. 4320 - 4326
Published: Feb. 9, 2024
A
highly
efficient
palladium-catalyzed
asymmetric
tandem
aza-Heck/Sonogashira
coupling
reaction
of
O-phenyl
hydroxamic
ethers
with
terminal
alkynes
is
described.
This
protocol
enables
versatile
access
to
challenging
chiral
isoindolinone
derivatives
bearing
a
quaternary
stereogenic
center.
The
aminoalkynylation
shows
broad
functional
group
tolerance
and
allows
the
straightforward
preparation
isoindolinones
high
efficiency
excellent
enantioselectivity
under
mild
conditions.
DFT
calculations
were
performed
disclose
mechanism
origins
enantioselectivity.
