The Chemical Record,
Journal Year:
2023,
Volume and Issue:
23(5)
Published: March 9, 2023
Abstract
Aryl
alkenes
represents
one
of
the
most
widely
occurring
structural
motif
in
countless
drugs
and
natural
products,
direct
C−H
functionalization
aryl
provides
atom‐
step
efficient
access
toward
valuable
analogues.
Among
them,
group‐directed
selective
olefinic
α
‐
β
‐C−H
functionalization,
bearing
a
directing
group
on
aromatic
ring,
has
attracted
remarkable
attentions,
including
alkynylation,
alkenylation,
amino‐carbonylation,
cyanation,
domino
cyclization
so
on.
These
transformations
proceed
by
endo
exo
−C−H
cyclometallation
provide
alkene
derivatives
excellent
site‐
stereo‐selectivity.
Enantio‐selective
were
also
covered
to
synthesis
axially
chiral
styrenes.
Organic Chemistry Frontiers,
Journal Year:
2022,
Volume and Issue:
9(8), P. 2109 - 2115
Published: Jan. 1, 2022
An
enantioselective
olefinic
C–H
alkenylation
using
transient
group
was
disclosed
to
afford
axially
chiral
aryl
1,3-dienes
in
up
99%
yields
and
>99%
ee.
The
derived
carboxylic
acid
efficient
ligand
asymmetric
alkylation.
Angewandte Chemie International Edition,
Journal Year:
2022,
Volume and Issue:
61(23)
Published: March 17, 2022
Axially
chiral
styrene-carboxylic
esters
were
synthesized
in
high
yields
with
excellent
enantioselectivity
by
the
cationic
rhodium(I)/H8
-BINAP
complex-catalyzed
chelation-controlled
[2+2+2]
cycloaddition
reactions
of
1,6-
and
1,7-diynes
1,3-enyne-carboxylic
esters.
The
diastereo-
enantioselective
synthesis
C2
symmetric
axially
cis
trans-stilbene-dicarboxylic
was
also
achieved
double
two
molecules
1,6-diyne
2,3-dialkynylmaleate
2,3-dialkynylfumarate,
respectively.
In
these
reactions,
coordinating
to
rhodium
a
five-membered
chelate
more
reactive
than
those
six-membered
chelate,
although
both
chelation
modes
realized
enantioselectivity.
enantioselection
mechanism
rhodium(I)-catalyzed
elucidated
DFT
calculations.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(30)
Published: May 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.
Organic Letters,
Journal Year:
2022,
Volume and Issue:
24(10), P. 1979 - 1984
Published: March 7, 2022
In
this
protocol,
an
efficient
palladium-catalyzed
asymmetric
synthesis
of
axially
chiral
conjugated
dienes
via
alkenyl
C-H
olefination
is
reported.
The
corresponding
atropisomeric
styrenes
containing
a
diene
scaffold
were
obtained
in
good
yields
with
enantioselectivities.
This
synthetic
strategy
features
easy
operation,
mild
reaction
conditions,
wide
functionality
tolerance,
and
high
efficiency.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(40)
Published: Aug. 16, 2023
Abstract
Axially
chiral
N
‐substituted
quinazolinones
are
important
bioactive
molecules,
which
presented
in
many
synthetic
drugs.
However,
most
strategies
toward
their
atroposelective
synthesis
mainly
limited
to
the
axially
arylquinazolinone
frameworks.
The
development
of
modular
methods
access
diverse
quinazolinone‐based
atropisomers
remains
scarce
and
challenging.
Herein,
we
report
regio‐
‐vinylquinazolinones
via
strategy
asymmetric
allylic
substitution‐isomerization.
catalysis
system
utilized
both
transition‐metal
organocatalysis
efficiently
afford
trisubstituted
tetrasubstituted
‐vinylquinazolinone
atropisomers,
respectively.
With
meticulous
design
β‐substituted
substrates,
Z
‐
E
‐tetrasubstituted
were
obtained
good
yields
high
enantioselectivities.
Organic Chemistry Frontiers,
Journal Year:
2022,
Volume and Issue:
9(18), P. 4834 - 4839
Published: Jan. 1, 2022
An
asymmetric
α-C–H
alkenylation
of
aryl
alkenes
has
been
disclosed
to
provide
axially
chiral
1,3-dienes,
proceeding
through
six-membered
exo
-cyclopalladation,
assisted
by
an
aldehyde/
l
-
t
-leucine
derived
transient
auxiliary.
Organic Letters,
Journal Year:
2024,
Volume and Issue:
26(27), P. 5670 - 5675
Published: June 26, 2024
Axially
chiral
carboxylic
acids
are
important
motifs
in
catalysts
and
ligands.
We
herein
reported
the
synthesis
of
axially
via
Pd(II)-catalyzed
atroposelective
C-H
olefination
using
acid
as
native
directing
group.
A
broad
range
axial
biaryl-2-carboxylic
were
synthesized
good
yields
with
high
enantioselectivities
(up
to
84%
yield
99%
ee).
Gram-scale
reaction
further
transformation
reactions
also
provide
a
platform
for
synthetic
applications
this
method.
Angewandte Chemie International Edition,
Journal Year:
2024,
Volume and Issue:
64(1)
Published: Nov. 7, 2024
Abstract
Precise
synthesis
of
carboxylic
acids
via
catalytic
carboxylation
with
CO
2
is
highly
appealing.
Although
considerable
advancements
have
been
achieved
in
difunctionalizing
unsaturated
hydrocarbons,
the
asymmetric
variants
are
conspicuously
underdeveloped,
particularly
addressing
axially
chiral
alkenes.
Herein,
we
report
first
atroposelective
alkynes
.
A
variety
valuable
obtained
good
yields
and
high
chemo‐,
regio‐,
Z/E
enantio‐selectivities.
Notably,
an
unexpected
anti
‐selective
carbo‐carboxylation
observed
sp
‐hybrid
carbo‐electrophile‐initiated
reductive
alkynes.
Mechanistic
studies
including
DFT
calculation
elucidate
origin
induction
‐selectivity
vinyl‐carboxylation
