Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(37), P. 7618 - 7622
Published: Jan. 1, 2024
A
novel
visible-light-driven
photoredox-catalyzed
cascade
bicyclization
of
1,7-enynes
with
aqueous
sulfoxonium
ylides
is
reported.
The
reaction
highly
chemoselective
three
new
C-C
bonds,
two
rings,
and
an
all-carbon
quaternary
stereocenter
constructed
in
a
one-pot
fashion.
This
mild
protocol
features
remarkably
broad
substrate
scope
good
functional
group
tolerance,
providing
general
practical
approach
to
access
various
cyclopenta[
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.
SynOpen,
Journal Year:
2023,
Volume and Issue:
07(04), P. 466 - 485
Published: Sept. 6, 2023
Abstract
Transition-metal-catalyzed
enantioselective
C–H
activation
provides
a
straightforward
strategy
to
synthesize
chiral
molecules
from
readily
available
sources.
In
this
graphical
review,
we
summarize
the
progress
on
half-sandwich
d6-metal
(CoIII,
RhIII,
IrIII,
RuII)-catalyzed
functionalization
reactions.
The
review
is
categorized
according
type
of
metal
catalyst
and
ligand
employed.
Representative
enantio-determining
models
catalytic
cycles
are
presented.
Angewandte Chemie,
Journal Year:
2024,
Volume and Issue:
136(17)
Published: Feb. 22, 2024
Abstract
The
development
of
new
methods
for
regio‐
and
stereoselective
activation
C−O
bonds
in
ethers
holds
significant
promise
synthetic
chemistry,
offering
advantages
terms
environmental
sustainability
economic
efficiency.
Moreover,
the
C−N
atropisomers
represent
a
fascinating
crucial
chiral
system,
extensively
found
natural
products,
pharmaceutical
leads,
frameworks
advanced
materials.
In
this
work,
we
have
introduced
nickel‐catalyzed
enantioselective
carbon‐oxygen
arylation
reaction
atroposelective
synthesis
N
‐arylisoquinoline‐1,3(2
H
,4
)‐diones.
high
regioselectivity
cleavage
benefits
from
stability
situ
formed
(amido)ethenolate
via
oxidative
addition.
Additionally,
self‐activation
aryl
bond
facilitates
under
mild
conditions,
leading
to
outstanding
enantioselectivities.
diverse
post‐functionalizations
axially
isoquinoline‐1,3(2
)‐diones
further
highlighted
utility
protocol
preparing
valuable
atropisomers,
including
phosphine
ligands.
Organic & Biomolecular Chemistry,
Journal Year:
2024,
Volume and Issue:
22(37), P. 7618 - 7622
Published: Jan. 1, 2024
A
novel
visible-light-driven
photoredox-catalyzed
cascade
bicyclization
of
1,7-enynes
with
aqueous
sulfoxonium
ylides
is
reported.
The
reaction
highly
chemoselective
three
new
C-C
bonds,
two
rings,
and
an
all-carbon
quaternary
stereocenter
constructed
in
a
one-pot
fashion.
This
mild
protocol
features
remarkably
broad
substrate
scope
good
functional
group
tolerance,
providing
general
practical
approach
to
access
various
cyclopenta[
