The Chemical Record,
Год журнала:
2023,
Номер
23(5)
Опубликована: Март 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.
Tetrahedron Chem,
Год журнала:
2022,
Номер
1, С. 100009 - 100009
Опубликована: Март 1, 2022
Axial
chirality
is
historically
epitomized
by
biaryl
compounds
containing
rotationally
impeded
aryl-aryl
linkage.
As
the
field
of
atroposelective
catalysis
advances,
synthesis
and
application
less
common
scaffolds
such
as
alkenes
have
now
come
to
fore.
The
manifestation
axial
in
aryl
was
hypothesized
1928
first
resolution
achieved
nearly
a
decade
later.
However,
catalytic
asymmetric
construction
axially
chiral
open-chain
appeared
only
2017
which
ushered
renewed
focus
on
these
structures.
In
principle,
possess
an
alkene
group
tethered
at
one
end
stereogenic
axis,
greatly
reduces
overall
rigidity.
To
date,
atropisomers
with
C
(vinyl)-C
(aryl)
(vinyl)-heteroatom
bond
been
reported.
Considering
rapid
growth
synthetic
utility
alkenes,
this
review
intends
provide
historical
overview
discusses
new
developments.
It
hope
that
timely
discussion
would
motivate
continued
nascent
field.
Chemical Reviews,
Год журнала:
2023,
Номер
123(17), С. 10641 - 10727
Опубликована: Авг. 28, 2023
Enantiomers,
where
chirality
arises
from
restricted
rotation
around
a
single
bond,
are
atropisomers.
Due
to
the
unique
nature
of
origins
their
chirality,
synthetic
strategies
access
these
compounds
in
an
enantioselective
manner
differ
those
used
prepare
enantioenriched
containing
point
arising
unsymmetrically
substituted
carbon
center.
In
particular
stereodynamic
transformations,
such
as
dynamic
kinetic
resolutions,
thermodynamic
and
deracemizations,
which
rely
on
ability
racemize
or
interconvert
enantiomers,
promising
set
transformations
optically
pure
late
stage
sequence.
Translation
approaches
with
atropisomers
requires
expanded
toolbox
for
epimerization/racemization
provides
opportunity
develop
new
conceptual
framework
synthesis
compounds.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
62(3)
Опубликована: Ноя. 25, 2022
Abstract
A
Cu/CPA
co‐catalytic
system
has
been
developed
for
achieving
the
direct
hydrophosphinylation
of
alkynes
with
phosphine
oxides
in
delivering
novel
axially
chiral
phosphorus‐containing
alkenes
high
yields
and
excellent
enantioselectivities
(up
to
99
%
yield
ee).
DFT
calculations
were
performed
elucidate
reaction
pathway
origin
enantiocontrol.
This
streamlined
modular
methodology
establishes
a
new
platform
design
application
styrene‐phosphine
ligands.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(24), С. 13476 - 13483
Опубликована: Июнь 10, 2023
A
novel
asymmetric
radical
strategy
for
the
straightforward
synthesis
of
atropisomerically
chiral
vinyl
arenes
has
been
established
herein,
proceeding
through
copper-catalyzed
atroposelective
cyanation/azidation
aryl-substituted
radicals.
Critical
to
success
relay
process
is
capture
highly
reactive
radicals
with
L*Cu(II)
cyanide
or
azide
species.
Moreover,
these
axially
vinylarene
products
can
be
easily
transformed
into
enriched
amides
and
amines,
enantiomerically
benzyl
nitriles
via
an
axis-to-center
chirality
transfer
process,
pure
organocatalyst
chemo-,
diastereo-,
enantioselective
(4
+
2)
cyclization
reaction.
Angewandte Chemie International Edition,
Год журнала:
2022,
Номер
61(25)
Опубликована: Апрель 25, 2022
Palladium(II)-catalyzed
C(alkenyl)-H
alkenylation
enabled
by
a
transient
directing
group
(TDG)
strategy
is
described.
The
dual
catalytic
process
takes
advantage
of
reversible
condensation
between
an
alkenyl
aldehyde
substrate
and
amino
acid
TDG
to
facilitate
coordination
the
metal
catalyst
subsequent
activation
tailored
carboxylate
base.
resulting
palladacycle
then
engages
acceptor
alkene,
furnishing
1,3-diene
with
high
regio-
E/Z-selectivity.
reaction
enables
synthesis
enantioenriched
atropoisomeric
2-aryl-substituted
1,3-dienes,
which
have
seldom
been
examined
in
previous
literature.
Catalytically
relevant
palladacycles
were
synthesized
characterized
X-ray
crystallography,
energy
profiles
step
stereoinduction
model
elucidated
density
functional
theory
(DFT)
calculations.
