Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(25), С. 16982 - 16989
Опубликована: Июнь 13, 2024
Catalytic
asymmetric
dearomatization
(CADA)
reactions
have
evolved
into
an
efficient
strategy
for
accessing
chiral
polycyclic
and
spirocyclic
scaffolds
from
readily
available
planar
aromatics.
Despite
the
significant
developments,
CADA
reaction
of
naphthalenes
remains
underdeveloped.
Herein,
we
report
a
Gd(III)-catalyzed
naphthalene
with
PyBox
ligand
via
visible-light-enabled
[4
+
2]
cycloaddition.
This
features
application
Gd/PyBox
complex,
which
regulates
reactivity
selectivity
simultaneously,
in
excited-state
catalysis.
A
wide
range
functional
groups
is
compatible
this
protocol,
giving
highly
enantioenriched
bridged
polycycles
excellent
yields
(up
to
96%)
>20:1
chemoselectivity,
dr,
>99%
ee).
The
synthetic
utility
demonstrated
by
2
mmol
scale
reaction,
removal
directing
group,
diversifications
products.
Preliminary
mechanistic
experiments
are
performed
elucidate
mechanism.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(33), С. 23457 - 23466
Опубликована: Июль 12, 2024
Developing
novel
strategies
for
catalytic
asymmetric
dearomatization
(CADA)
reactions
is
highly
valuable.
Visible
light-mediated
photocatalysis
demonstrated
to
be
a
powerful
tool
activate
aromatic
compounds
further
synthetic
transformations.
Herein,
dearomative
[2
+
2]
photocycloaddition/ring-expansion
sequence
of
indoles
with
simple
alkenes
was
reported,
providing
facile
access
enantioenriched
cyclopenta[
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Фев. 16, 2024
Abstract
Small
molecules
with
conformationally
rigid,
three-dimensional
geometry
are
highly
desirable
in
drug
development,
toward
which
a
direct,
simple-to-complexity
synthetic
logic
is
still
of
considerable
challenges.
Here,
we
report
intermolecular
aza-[2
+
2]
photocycloaddition
(the
aza-Paternò–Büchi
reaction)
indole
that
facilely
assembles
planar
building
blocks
into
ladder-shape
azetidine-fused
indoline
pentacycles
contiguous
quaternary
carbons,
divergent
head-to-head/head-to-tail
regioselectivity,
and
absolute
exo
stereoselectivity.
These
products
exhibit
marked
three-dimensionality,
many
possess
3D
score
values
distributed
the
highest
0.5%
region
reference
to
structures
from
DrugBank
database.
Mechanistic
studies
elucidated
origin
observed
regio-
stereoselectivities,
arise
distortion-controlled
C-N
coupling
scenarios.
This
study
expands
repertoire
energy
transfer
catalysis
for
accessing
structurally
intriguing
architectures
high
molecular
complexity
underexplored
topological
chemical
space.
Nature Communications,
Год журнала:
2024,
Номер
15(1)
Опубликована: Март 19, 2024
Abstract
Medium-sized-ring
compounds
have
been
recognized
as
challenging
synthetic
targets
in
organic
chemistry.
Especially,
the
difficulty
of
synthesis
will
be
augmented
if
an
E
-olefin
moiety
is
embedded.
Recently,
photo-induced
dearomative
cycloaddition
reactions
that
proceed
via
energy
transfer
mechanism
witnessed
significant
developments
and
provided
powerful
methods
for
transformations
are
not
easily
realized
under
thermal
conditions.
Herein,
we
report
intramolecular
[5
+
4]
naphthalene-derived
vinylcyclopropanes
visible-light
irradiation
a
proper
triplet
photosensitizer.
The
reaction
affords
dearomatized
polycyclic
molecules
possessing
nine-membered-ring
with
good
yields
(up
to
86%)
stereoselectivity
8.8/1
/
Z
).
Detailed
computational
studies
reveal
origin
behind
favorable
formation
thermodynamically
less
stable
isomers.
Diverse
derivations
products
also
demonstrated.
