Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(30)
Опубликована: Май 25, 2023
Abstract
Hydrofunctionalization
of
alkynes
is
one
the
most
efficient
ways
to
access
axially
chiral
styrenes
with
open‐chained
olefins.
While
great
advances
have
been
achieved
for
1‐alkynylnaphthalen‐2‐ols
and
analogues,
atroposelective
hydrofunctionalization
unactivated
internal
lags.
Herein
we
reported
a
platinum‐catalyzed
hydrosilylation
first
time.
With
monodentate
TADDOL‐derived
phosphonite
L1
used
as
ligand,
various
were
in
excellent
enantioselectivities
high
E
‐selectivities.
Control
experiments
showed
that
N
H‐arylamide
groups
significant
effects
on
both
yields
could
act
directing
groups.
The
potential
utilities
products
shown
by
transformations
amide
motifs
products.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(10)
Опубликована: Янв. 4, 2023
Herein,
we
report
a
synthesis
of
cyclohexanones
bearing
multi-continuous
stereocenters
by
combining
copper-catalyzed
asymmetric
conjugate
addition
dialkylzinc
reagents
to
cyclic
enones
with
iridium-catalyzed
allylic
substitution
reaction.
Good
excellent
yields,
diastereoselectivity
and
enantioselectivity
can
be
obtained.
Unlike
the
stereodivergent
construction
adjacent
(1,2-position)
reported
in
literature,
current
reaction
achieve
nonadjacent
(1,3-position)
proper
combination
two
chiral
catalysts
different
enantiomers.
ACS Catalysis,
Год журнала:
2023,
Номер
13(6), С. 3841 - 3846
Опубликована: Март 3, 2023
Catalytic
asymmetric
hydrofunctionalization
of
alkenes
is
a
well-established
method
with
which
to
construct
complex
C(sp3)-enriched
molecules
central
chirality.
In
contrast,
the
use
catalytic
abundant
alkyne
substrates
produce
valuable
multisubstituted
axial
chirality
remains
largely
unexplored.
Here,
we
report
general
procedure
this
type
catalyzed
by
Ni(II)
salts
and
employing
structurally
simple
chiral
PyrOx
ligand.
A
wide
variety
diverse
atropisomeric
styrenes
have
been
obtained
from
hydroarylation
alkynes
high
efficiency,
complete
Z-selectivity,
excellent
enantioselectivity.
Angewandte Chemie International Edition,
Год журнала:
2023,
Номер
62(32)
Опубликована: Июнь 15, 2023
Abstract
Asymmetric
cross‐couplings
based
on
1,2‐carbon
migration
from
B‐ate
complexes
have
been
developed
efficiently
to
access
valuable
organoboronates.
However,
enantioselective
reactions
triggered
by
1,2‐boron
shift
remained
be
unaddressed
synthetic
challenge.
Here,
Ir‐catalyzed
asymmetric
allylic
alkylation
enabled
was
developed.
In
this
reaction,
we
disclosed
that
excellent
enantioselectivities
were
achieved
through
an
interesting
dynamic
kinetic
resolution
(DKR)
process
of
carbonates
at
the
elevated
temperature.
Notably,
highly
(bis‐boryl)alkenes
array
diversifications
versatile
molecules.
Extensive
experimental
and
computational
studies
conducted
elucidate
reaction
mechanism
DKR
clarify
origin
enantioselectivities.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
unknown
Опубликована: Июль 23, 2024
Abstract
Catalytic
enantioselective
preparation
of
alkene
atropisomers
with
multiple
stereogenic
elements
and
discovery
their
applications
have
become
significant
but
challenging
issues
in
the
scientific
community
due
to
unique
structures
this
class
atropisomers.
We
herein
report
first
catalytic
atroposelective
cyclopentenyl[
b
]indoles,
a
new
kind
atropisomers,
point
axial
chirality
via
an
unusual
rearrangement
reaction
3‐indolylmethanols
under
asymmetric
organocatalysis.
Notably,
novel
type
promising
developing
chiral
ligands
or
organocatalysts,
discovering
antitumor
drug
candidates
fluorescence
imaging
materials.
Moreover,
theoretical
calculations
elucidated
possible
mechanism
non‐covalent
interactions
control
enantioselectivity.
This
approach
offers
synthetic
strategy
for
elements,
represents
3‐indolylmethanols,
which
will
advance
chemistry
indole
chemistry.
Journal of the American Chemical Society,
Год журнала:
2021,
Номер
143(43), С. 17989 - 17994
Опубликована: Окт. 20, 2021
Here
we
report
that
a
palladium(0)
complex
can
mediate
the
unprecedented
intermolecular
coupling
reaction
of
1,3-enynes
and
N-sulfonylimines
regio-
stereoselectively,
resultant
palladium(II)
species
undergo
cascade
Suzuki
with
organoboronic
reagents.
The
substrate
scope
is
substantial
for
asymmetric
three-component
process,
enantioenriched
all-carbon
tetra-substituted
alkene
derivatives
are
efficiently
constructed
in
modular
cis-difunctionalized
manner.
Control
experiments
density
functional
theory
(DFT)
calculations
support
idea
acts
as
π-Lewis
base
catalyst
by
chemoselectively
forming
η2-complexes
moiety
1,3-enynes,
thus
increasing
nucleophilicity
alkyne
group
based
on
principle
vinylogy,
to
attack
imines
enantioselectively.
preferable
formation
aza-palladacyclopentene
intermediates,
via
90°
single
bond
rotation
from
π-allyl
complex,
guarantees
formal
cis-carbopalladation
group.
In
addition,
palladium(0)-catalyzed
enantioselective
reductive
1,3-enyne
imine
realized
using
formic
acid
hydrogen
transfer
reagent.
Organic Letters,
Год журнала:
2021,
Номер
23(21), С. 8132 - 8137
Опубликована: Окт. 14, 2021
A
weakly
coordinated
carboxylate-directed
palladium-catalyzed
atroposelective
C-H
alkynylation
method
for
the
development
of
novel
axially
chiral
styrene-type
carboxylic
acids
is
disclosed.
This
transformation
exhibits
good
yields
(up
to
85%),
excellent
enantiocontrol
99%
ee),
and
mild
conditions.
Notably,
synthetic
utility
resulting
alkynyl
acid
derivatives
was
demonstrated
by
various
derivatizations
as
well
their
potential
ligands
in
asymmetric
activations.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(45)
Опубликована: Сен. 16, 2022
The
application
of
Suzuki-Miyaura
coupling
reaction
to
forge
the
atropisomeric
biaryls
has
seen
remarkable
progress
but
exploration
this
chemistry
directly
chiral
C(aryl)-C(alkene)
axis
is
underdeveloped.
replacement
arene
substrates
by
alkenes
intensifies
challenges
in
terms
reactivity,
configurational
atropostability
product
and
selectivity
control.
By
meticulous
ligand
design
fine-tuning
parameters,
we
identified
a
highly
active
3,3'-triphenylsilyl-substituted
phosphite
realize
arene-alkene
hindered
aryl
halides
vinyl
boronates
under
very
mild
conditions.
axially
acyclic
aryl-alkenes
were
generated
commendable
efficiency,
enantioselectivity
E/Z
selectivity.
