Advanced Synthesis & Catalysis,
Journal Year:
2023,
Volume and Issue:
365(9), P. 1398 - 1404
Published: April 12, 2023
Abstract
Herein,
we
present
a
chiral
boro‐phosphate
catalyzed
atroposelective
asymmetric
transfer
hydrogenation
method,
leading
to
family
of
axially
styrene‐type
allylalcohols.
This
dynamic
kinetic
resolution
approach
portrays
simple
procedure,
mild
conditions
and
good
enantiocontrol
(51–95%
ee),
thus
providing
an
important
alternative
assemble
the
challenging
atropisomeric
aryl‐acyclic
alkene
scaffolds.
magnified
image
Nature Communications,
Journal Year:
2023,
Volume and Issue:
14(1)
Published: Nov. 3, 2023
The
formal
C-C
bond
insertion
into
aldehydes
is
an
attractive
methodology
for
the
assembly
of
homologated
carbonyl
compounds.
However,
homologation
has
been
limited
to
diazo
approach
and
enantioselective
reaction
was
rarely
developed.
Herein,
we
report
asymmetric
through
diyne
cyclization
strategy.
In
presence
Cu(I)/SaBOX
catalyst,
this
method
leads
efficient
construction
versatile
axially
chiral
naphthylpyrroles
in
moderate
excellent
yields
with
good
enantioselectivities.
This
protocol
represents
a
rare
example
using
non-diazo
approach.
combined
experimental
computational
mechanistic
studies
reveal
mechanism,
origin
regioselectivity
stereoselectivity.
Notably,
phosphine
ligand
derived
from
synthesized
skeleton
proven
be
applicable
catalysis.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
62(16)
Published: Feb. 16, 2023
We
have
developed
the
Rh+
/H8
-binap-catalyzed
chemo-,
regio-,
diastereo-,
and
enantioselective
intermolecular
[2+2+2]
cycloaddition
of
three
unsymmetric
2π
components.
Thus,
two
arylacetylenes
react
with
a
cis-enamide
to
yield
protected
chiral
cyclohexadienylamine.
Moreover,
replacing
one
arylacetylene
silylacetylene
enables
distinct
These
transformations
proceed
excellent
selectivity
(complete
regio-
diastereoselectivity
up
>99
%
ee).
Mechanistic
studies
suggest
chemo-
regioselective
formation
rhodacyclopentadiene
intermediate
from
terminal
alkynes.
Organic Chemistry Frontiers,
Journal Year:
2024,
Volume and Issue:
11(10), P. 2857 - 2863
Published: Jan. 1, 2024
A
Rh-catalyzed
neighboring
group-directed
asymmetric
[2
+
2
2]
cycloaddition
of
1,6-diynes
and
ynamides
to
generate
C–N
axially
chiral
indole
derivatives
has
been
developed.
The Journal of Organic Chemistry,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 13, 2025
A
series
of
polyaryl-substituted
fluoranthenes
is
built
in
good
to
excellent
yields
via
Earth-abundant
metal-catalyzed
[2
+
2+
2]
cycloaddition
1,6-diynes
with
alkynes
developed.
This
method
runs
smoothly
using
a
cheap
catalytic
system
(CoI2/dppe/Zn)
as
the
catalyst.
Generally,
this
strategy
exhibits
low
cost,
high
efficiency,
atom
economy,
and
functional
group
tolerance.
Additionally,
both
terminal
alkynes,
especially
heteroaryl-substituted
acetylenes,
internal
alkyne,
tolerate
work.
Furthermore,
photophysical
properties
selected
also
investigated.
Organic Letters,
Journal Year:
2025,
Volume and Issue:
unknown
Published: March 27, 2025
Herein,
we
describe
an
efficient
copper-catalyzed
cyclization
of
triynes
via
vinyl
cation
intermediates.
The
reaction
leads
to
the
practical
and
atom-economical
synthesis
valuable
polycyclic
pyrroles
by
constructing
three
new
rings
in
one
step
under
mild
conditions.
proposed
mechanism
shows
ordered
regioselective
alkynes.
Moreover,
possibility
such
asymmetric
triyne
also
emerges.
Angewandte Chemie International Edition,
Journal Year:
2023,
Volume and Issue:
63(1)
Published: Nov. 16, 2023
Abstract
Axially
chiral
open‐chained
olefins
are
an
underexplored
class
of
atropisomers,
whose
enantioselective
synthesis
represents
a
daunting
challenge
due
to
their
relatively
low
racemization
barrier.
We
herein
report
rhodium(I)‐catalyzed
hydroarylative
cyclization
1,6‐diynes
with
three
distinct
classes
arenes,
enabling
highly
broad
range
axially
1,3‐dienes
that
conformationally
labile
(Δ
G
≠
(
rac
)=26.6–28.0
kcal/mol).
The
coupling
reactions
in
each
category
proceeded
excellent
enantioselectivity,
regioselectivity,
and
Z/E
selectivity
under
mild
reaction
conditions.
Computational
studies
the
quinoline
N
‐oxide
system
reveal
proceeds
via
initial
oxidative
1,6‐diyne
give
rhodacyclic
intermediate,
followed
by
σ‐bond
metathesis
between
arene
C−H
bond
Rh−C(vinyl)
bond,
subsequent
C−C
reductive
elimination
being
enantio‐determining
turnover‐limiting.
DFT‐established
mechanism
is
consistent
experimental
studies.
coupled
products
‐oxides
undergo
facile
visible
light‐induced
intramolecular
oxygen‐atom
transfer,
affording
epoxides
complete
axial‐to‐central
chirality
transfer.
