Research Square (Research Square),
Journal Year:
2024,
Volume and Issue:
unknown
Published: Aug. 16, 2024
Abstract
The
enantioselective
domino
Heck/cross-coupling
has
emerged
as
a
powerful
tool
in
modern
chemical
synthesis
for
decades.
Despite
significant
progress
relative
rigid
skeleton
substrates,
the
implementation
of
asymmetric
cascades
highly
flexible
haloalkene
substrates
remains
challenging
and
long-standing
goal.
Here
we
report
an
efficient
tandem
Heck/Tsuji−Trost
reaction
vinylic
halides
with
1,3-dienes
enabled
by
palladium
catalysis.
A
variety
functional
cyclic
isoprenoids,
which
are
key
structural
motifs
numerous
natural
products
family,
were
delivered
good
yields
excellent
regio-,
diastereo-
enantioselectivity.
Specifically,
Heck
insertion
stereodetermining
step
to
form
ƞ3
π-allyl
complex
situ
trapping
nucleophiles
enable
Heck/etherification
formal
(4+2)
cycloaddition
manner.
Engineering
Sadphos
bearing
androgynous
non-C2-symmetric
chiral
sulfinamide
phosphine
ligands
vital
component
achieving
catalytic
reactivity
This
strategy
offers
general,
modular
divergent
platform
rapidly
upgrading
feedstock
dienes
various
value-added
molecules
is
expected
inspire
development
other
Heck/cross-couplings.
ACS Catalysis,
Journal Year:
2024,
Volume and Issue:
14(22), P. 17039 - 17045
Published: Nov. 4, 2024
Herein,
we
demonstrate
the
successful
application
of
reductive
[2
+
4]
annulation
in
atroposelective
de
novo
benzene
ring
formation.
This
nickel-catalyzed
reaction
between
β-substituted
α-naphthylalkynes
and
a
biselectrophile
C(sp2)–X
type
offers
an
efficient
convenient
method
to
prepare
highly
enantioenriched
C1-symmetric
axially
chiral
biaryls
containing
two
preinstalled
functionalities.
The
coupling
products
can
be
used
as
versatile
synthetic
intermediates
access
bidentate
ligands
or
bifunctional
organocatalysts,
their
utility
asymmetric
catalysis
is
also
showcased
this
context.
