The Journal of Organic Chemistry,
Journal Year:
2024,
Volume and Issue:
89(11), P. 7630 - 7643
Published: May 13, 2024
Atropoisomeric
chemotypes
of
diaryl
ethers-related
scaffolds
are
prevalent
in
naturally
active
compounds.
Nevertheless,
there
remains
considerable
research
to
be
carried
out
on
the
catalytic
asymmetric
synthesis
these
axially
chiral
molecules.
In
this
instance,
we
disclose
an
N-heterocyclic
carbene
(NHC)-catalyzed
ethers
via
atroposelective
esterification
dialdehyde-containing
ethers.
NHC
desymmetrization
produces
ether
atropisomers
with
high
yields
and
enantioselectivities
moderate
circumstances.
Chiral
compounds
may
precursors
for
highly
functionalized
bioactivity
ligands
catalysis.
Nature Communications,
Journal Year:
2024,
Volume and Issue:
15(1)
Published: April 16, 2024
Abstract
The
past
century
has
witnessed
a
large
number
of
reports
on
the
Z
/
E
isomerization
alkenes.
However,
vast
majority
them
are
still
limited
to
di-
and
tri-substituted
stereospecific
tetrasubstituted
alkenes
remains
be
an
underdeveloped
area,
thus
lacking
in
stereodivergent
synthesis
axially
chiral
Herein
we
report
atroposelective
alkene
analogues
by
asymmetric
allylic
substitution-isomerization,
followed
their
via
triplet
energy
transfer
photocatalysis.
In
this
regard,
N
-vinylquinolinones
is
achieved
efficiently.
Mechanistic
studies
indicate
that
benzylic
radical
generation
distribution
two
key
factors
for
preserving
enantioselectivities
compounds.
ACS Catalysis,
Journal Year:
2023,
Volume and Issue:
13(6), P. 3841 - 3846
Published: March 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.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(24), P. 13476 - 13483
Published: June 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,
Journal Year:
2023,
Volume and Issue:
62(21)
Published: March 22, 2023
A
copper-catalyzed
atroposelective
ring-opening
reaction
of
cyclic
diaryliodoniums,
sodium
cyanate
(NaOCN)
and
phenols
is
reported.
The
chemoselectively
affords
axially
chiral
carbamates
by
sequential
coupling
diaryliodonium
NaOCN,
followed
phenol.
Mechanistic
investigations
revealed
that
phenol
not
only
a
reagent
to
trap
highly
active
intermediate
isocyanates,
but
it
also
activates
the
copper
catalyst
as
standby
ligand.
were
readily
transformed
into
functionalized
urea
derivatives
within
simple
nucleophilic
substitution
reaction.
